286 INDUSTRIAL AND ENGINEERING CHEMISTRY Yol. 21, No.

Preparation and Properties of the Ammonium

Phosphates1
Wm. H. Ross, Albert R. Merz, and K. D. Jacob
Bureau of Chemistry and Soils. Washington, D. C.

products of the re-· The most concentrated fertilizer materials obtain- with ammonium sulfide.
able are salts in which both the acid and basic radicals
THE action between phos-
phoric oxide and water contain the essential fertilizer elements. The am-
These salts are soluble in
water and are crystallizable.
are meta-, pyro-, and ortho- monium phosphates form an important group of such Ammonium trimetaphos-
phosphoric acids. These concentrated fertilizer compounds. They form three
phate is prepared from micro-
5

acids combine with ammonia series of salts—the meta-, pyro-, and ortho-phosphates cosmic salt by subjecting it
directly to form three groups of ammonium. Methods for their preparation are to gentle heating until the
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of salts known as the meta-, described and their properties outlined, particular fused mass begins to crystal-
pyro-, and ortho-phosphates attention being paid to those compounds which give lize and changes into insoluble
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of ammonium. These salts promise of extensive utilization in commercial con-
may be produced also by centrated fertilizers.
double decomposition be-
tween ammonium salts and corresponding phosphates of other
bases. Both methods of preparation are comparatively simple
in operation, and the economic production of any ammonium
phosphate is therefore largely a question of the cost of produc-
ing the phosphoric acid required in its manufacture.
Ammonium
Metaphosphates
The ordinary metaphosphoric acid, or glacial phosphoric
acid, is a transparent, non-crystalline, vitreous solid, which
rapidly absorbs moisture from the air, and in solution com-
bines with water to form orthophosphoric acid. The rate
of change into the ortho acid increases with rise in tempera-
ture and with the concentration of the solution. Strong
mineral acids accelerate the change while weak organic acids
retard the speed of conversion. The usual method of prepar-
ing the acid consists in adding the proper proportion of water
to phosphorus pentoxide, or in calcining orthophosphoric
acid at about 300° C. The product prepared by either of
these methods is a mixture of a series of metaphosphoric acids
having molecular formulas which are multiples of the first
of the series. These are known as monometaphosphoric
acid, dimetaphosphoric acid, etc. The first in the series is
monobasic, and the remainder polybasic. A large number of
alkali metaphosphates is thus theoretically possible, but their
preparation in a pure state is very difficult, owing to their
instability and to the fact that they do not readily crystallize.
Neutralization of glacial phosphoric acid with an alkali
will give alkali metaphosphates of the series of metaphosphoric
acids present. A similar mixture of alkali metaphosphates
is also obtained on calcining the corresponding monoalkali
orthophosphate. Thus one or more of the ammonium meta-
phosphates may be obtained in mixture with metaphosphoric
acid by heating monoammonium phosphate at about 300° C.
Ammonium monometaphosphate may be prepared by
neutralizing a solution of metaphosphoric acid in the cold
with ammonium carbonate.2 The monometaphosphates are
sparingly soluble in water and do not readily crystallize.
Ammonium di-3 and tetra-4 metaphosphates are obtained
on heating phosphoric acid with a heavy metal, such as
copper or lead, at 350° C., and then decomposing the product
Presented
1
part of the Symposium on "Concentrated Fertilizers
as
and Fertilizer Materials" before the Division of Fertilizer Chemistry at the
76th Meeting of the American Chemical Society, Swampscott, Mass., Sep-
tember 10 to 14, 1928.
2
Tammann, J. prakt. Chem., [2] 46, 431 (1892); Z. physik. Chem., 6,
125 (1890).
8
Fleitmann, Pogg. Ann., 78, 233, 338 (1849).
4
Warschauer, Z. anorg. Chem., 36, 137 (1903).
sodium monometaphosphate
and soluble sodium trimeta-
phosphate. The latter is
then treated with an ammonium salt for the preparation of
ammonium trimetaphosphate by double decomposition.
Ammonium pentametaphosphate2 may be prepared by
heating ammonium dimetaphosphate at 200-250° C., treating
the resulting mass with cold water, and adding alcohol to
precipitate ammonium pentametaphosphate. On treating
this compound with a potash salt, it may be changed in
turn to a compound having the formula NH4K4P5OU.6H2O.
This compound is of no commercial application at present,
but it is of interest in that it affords an example of a definite
chemical compound which contains all three of the fertilizer
elements.
Ammonium Pyrophosphates
Pyrophosphoric acid is the first member of a series of
polyphosphoric acids. Formulas of these acids are multiples
of orthophosphoric acid less one or more molecules of water.
Pyrophosphoric acid (diphosphoric acid) may be prepared by
heating equal molecular proportions of ortho- and meta-
phosphoric acids at 100° C., or by adding lead acetate to a
solution of an alkali pyrophosphate and decomposing the pre-
cipitated lead pyrophosphate with hydrogen sulfide.
Pyrophosphoric acid is a tetrabasic acid and is theoretically
capable of forming four salts according as one or more of the
hydrogen ions of the acid is replaced with a base. The normal
or tetraammonium pyrophosphate,6 ( 4), 2 7, separates
as a crystalline salt when alcohol is added to a solution of
pyrophosphoric acid saturated with ammonia. The salt is
very soluble in water, reacts alkaline, and is unstable.
The secondary ammonium pyrophosphate, (NH4)2H2P207,
may be prepared in solution by adding ammonia to pyro-
phosphoric acid urftil the solution reacts alkaline to methyl
orange. It may be obtained in the solid state6 by dissolving
the tetrapyrophosphate in acetic acid, mixing with alcohol,
and allowing to stand until crystallization occurs, or by
heating ammonium orthophosphate at 155° C. This salt
is neutral to methyl orange but acid to phenolphthalein, and
if kept dry may be stored indefinitely without change. The
primary and tertiary salts have not been prepared in a solid
state.
Ammonium Orthophosphates
Orthophosphoric acid differs from the meta and pyrg acids
in being stable in contact with water at ordinary tempera-
8
Lindborn, Ber., 8, 122 (1875); Von Knorre, Z. anorg. Chem., 24, 369
(1900).
8
Schwarzenberg, Liebig’s Ann., 66, 141 (1848).
March, 1929 INDUSTRIAL AND ENGINEERING CHEMISTRY 287

tures. This is also true of the salts formed from the ortho phosphates. They show, for example, (1) that in order to
acid with non-volatile bases, and the orthophosphates are make separate precipitations of the mono-, di-, and tri-
practically the only salts of phosphoric acid which occur in ammonium phosphates, it is necessary to maintain the am-
nature. monia pressure respectively below, between, and above the
Properties—Orthophosphoric acid is a tribasic acid, and equilibrium pressures of Equations 1 and 2; and (2) that in
it therefore reacts with ammonia to form three ammonium order to prevent the dissociation of diammonium phosphate
phosphates known as the mono, di, and tri compounds. or triammonium phosphate in solution, it is necessary to
Monoammonium phosphate is slightly acid in reaction; maintain an ammonia pressure equal to that which is in
diammonium phosphate, slightly*alkaline; asid triammonium equilibrium with each of the respective salts alone in solution.
phosphate, strongly alkaline. The stability of these three It has been shown that this pressure in the case of diam-
compounds decreases in the order named. monium phosphate is above the equilibrium ammonia pres-
The manner in which the di- and tri-ammonium phosphates sure of Equation 1, and therefore above the pressure required
dissociate is represented by the following reactions: to prevent the dissociation of diammonium phosphate in the
solid state. It follows, therefore, that diammonium phos-
(NH4)2HPC)4 =
NH4H2P04 + NH3 (1)
(NH4)3P04 =
(NH4)2HP04 + NH3 (2) phate loses ammonia more rapidly in solution than in the
solid form, unless it has a sufficient quantity of the mono-
Each of these systems is one of two components and three phosphate mixed with it to make the solution saturated with
phases, and consequently at a given temperature there is respect to both salts. The stability of diammonium phos-
but one pressure of ammonia at which both solids can exist in phate when stored in a damp place may therefore be increased
equilibrium. It follows, therefore, that if solid monoammo- by mixing it with a quantity of monoammonium phosphate.
nium phosphate is placed in a closed vessel and ammonia is Table I shows that diammonium phosphate is the most
added at constant temperature, no reaction will take place soluble of the three phosphates and triammonium phosphate
until the pressure of the ammonia reaches that corresponding the least. The solubility of the triammonium phosphate de-
to the equilibrium pressure of Equation 1. Chemical reaction creases rapidly with excess of ammonia and amounts to only
between ammonia and the mono salt will then begin to take 0.16 gram per 100 grams of solvent when dissolved in an
place with formation of the di salt. Further additions of ammonia solution of 0.90 specific gravity. It is therefore
ammonia will be followed with no further change in pressure precipitated as a white, crystalline salt when sufficient gaseous
until the monophosphate has been completely changed into ammonia or a strong ammonia solution is added to a saturated
the diphosphate. The addition of more ammonia will then solution of either of the other compounds. It may be
be followed in turn with further increase in pressure but with- obtained in a dry state by passing a stream of ammonia
out chemical change until the equilibrium pressure of Equation over the material in a closed vessel at 90-100° C. The dry
2 is reached. Formation of the tri compound will then take salt changes into the di compound with loss of ammonia at
place by reaction between the ammonia and the di compound. ordinary temperatures. Addition of water increases the rate
Table I—Properties of Ammonium Orthophosphates
•
Heat of
Solubility Forma-
at 25° C. TION from Ammonia pH of
per 100 Gaseous Vapor 0.1 M
Crystal Grams NHj and Pressure Soln. Reaction of 0.1 M Soln.
Compound Form Water Solid H3PO4 100° C. 125° C. to Indicators
Grams Cal. Mm. Hg. Mm. Hg.
Monoammonium phosphate, NH4H2PO4 Tetragonal 40,0 29,000 0.00 0.05 4.4 Alkaline to methyl orange; red to methyl red
Diammonium phosphate, (NH4)2HPC>4 Monoclinic 69.5 48,500 5.0 30.0 8.0 Neutral to cresol red
Triammonium phosphate, (NH4)aP04 Orthorhombic 17.7 58,400 643 1177 9.4 Neutral to thymol blue in alkaline range

The situation is somewhat different when ammonia is added of dissociation. A solution of diammonium phosphate also
to a saturated solution of monoammonium phosphate in loses ammonia, but very slowly, at ordinary temperatures.
contact with the solid salt. The addition of ammonia is No appreciable loss occurs if the solid is kept dry or mixed
followed by increase in pressure, but as the system is now with the mono salt as already explained.
divariant, diammonium phosphate begins to form immedi- Table II—Solubility of Monoammonium Phosphate and of Am-
ately. The solution will then be saturated with respect to monium Sulfate
the mono salt, but with increasing concentrations of the di Temperature NH4H2PO4 (NHilzSOV
°

salt, until it becomes saturated with respect to both salts. C.

0
Grams per 100 grams water
19.9 70.6
The ammonia pressure will then correspond to the equilibrium 23.6 71.8
10 27.4 73.0
pressure of Equation 1, or to the pressure at which diam- 20 35.8 75.4
monium phosphate is formed in the dry state. Further ad- 30 45.3 78.0
40 56.2 81.0
dition of ammonia brings about the conversion of the solid 60 83.3 88.0
80 121.0 95.3
monophosphate into the diphosphate without change in 100 177.2 103.3
pressure until the solid consists only of the di salt. An in- °
Seidell, "Solubilities of Inorganic and Organic Compounds," 2nd Ed., p. 63.
crease in pressure will now follow any further addition of
ammonia and the concentration of the mono salt in the liquid Preparation—The results given in Table II show that
phase will decrease until at a certain pressure the solution con- monoammonium phosphate is less soluble than ammonium
tains only the diphosphate. This pressure is of interest in sulfate at ordinary temperatures, but more soluble at 100° C.
that it is the pressure required to prevent dissociation of At 65° C. the solubility of the two salts is about the same.
diammonium phosphate when this salt is dissolved in water. This similarity between the solubility of the two salts at
The addition of more ammonia will be followed by the forma- this temperature is no doubt responsible in a large measure
tion of the triphosphate with corresponding changes in the for the widespread view that a sulfate of ammonia plant can
solid and liquid phases until the transformation of the di be so constructed and erected as to be available without alter-
into the tri salt is complete. ation for the production of monoammonium phosphate from
These pressure relationships are of practical application in concentrated phosphoric acid and ammonia.7 This would
a study of the properties and preparation of the ammonium 7
Ernst and Edwards, Ind. Eng. Chbm., 19, 768 (1927).
 288 INDUSTRIAL AND ENGINEERING CHEMISTRY
no doubt be true if the purity of the acid used compared with
that of commercial sulfuric acid. Crude phosphoric acid,
particularly that prepared by the sulfuric acid method, differs
from commercial phosphoric acid in that it contains a con-
siderable proportion of iron and aluminum phosphates which
are precipitated as a gelatinous sludge when the acid is
neutralized with ammonia. The formation of this sludge
greatly interferes in the preparation of ammonium phosphate
by any method which depends upon the continuous removal
of the crystallized salts as in the saturator method of pre-
paring ammonium sulfate.
A saturator temperature of 60-65° C. gives best results
when preparing ammonium sulfate from by-product ammonia,
but when strong ammonia gas is used an increase in tempera-
ture to 100° C. is recommended7 in order that excess water
may be eliminated as steam. The solubility of monoammo-
nium phosphate at this temperature amounts to 63.9 grams per
100 grams of solution, compared with 50.8 grams for ammo-
nium sulfate. A 5-degree drop in the temperature of the
latter solution will therefore deposit only 0.4 part of salt per
100 parts of solution, but the salt deposited in the same tem-
perature drop of a saturated monoammonium phosphate
solution will be more than five times as great. Monoammo-
nium phosphate also differs from ammonium sulfate in that its
crystals grow more rapidly and show a greater tendency to
knit together. Danger from clogging in the continuous
operation of a saturator with monoammonium phosphate
will therefore be greater than with ammonium sulfate.
In the process now generally used for preparing crude
monoammonium phosphate for fertilizer purposes, the crude
acid is rapidly neutralized with ammonia in open vessels to
the point where the solution reacts yellow to methyl orange
and red to methyl red. The heat of the reaction is sufficient
to raise the temperature of the liquid to the boiling point and
bring about some loss of water by evaporation, but the con-
centration that takes place is not sufficient to saturate the
solution at the boiling temperature. The iron and aluminum
phosphates present precipitate out, however, to form a
slurry which is difficult to filter. The whole mass is accord-
ingly reduced to dryness by feeding it into a rotary kiln that
is maintained at a temperature below 120° C.
In the preparation of technical monoammonium phosphate,
use is made of a refined acid. This is added, with the equiva-
lent amount of ammonia, to the mother liquor from a previous
batch until the solution becomes nearly saturated at the tem-
perature to which it is raised by the heat of the reaction. The
solution is then allowed to cool in a crystallizer of the Walker
type, and the crystallized salts are recovered by centrifug-
ing.
A similar process is used in the preparation of diammonium
phosphate8 from concentrated phosphoric acid produced by
the volatilization method. The acid is first added to a solu-
tion of the salt saturated at room temperature until the solu-
tion changes the color of bromocresol purple, or until the P2O5
content of the solution is increased by about one-third.
Gaseous ammonia and the phosphoric acid are then added si-
multaneously in the proportion of 1.5 mols of the former to 1
of the latter, and at such a rate that the temperature does
not exceed 80-90° C. The addition of the ammonia and
phosphoric acid is continued until the phosphate content of
the solution is approximately doubled. The solution is then
cooled to room temperature and ammonia added until a
diluted portion of the solution reacts neutral to cresol red.
The coarse monoclinic crystals of diammonium phosphate
which separate from solution under these conditions are
centrifuged and then dried at 60° C. and the mother liquor
is added to the next batch for use again in the process.
s Griessbach, Balz, and Rossler, U. S. Patent 1,670,504 (1928),
Vol. 21, No. 3
A modification of this process for which patents are now
pending nas been developed in this country and also adopted
in Europe. The production of diammonium phosphate for
use as a fertilizer offers an advantage over the mono compound
in that it contains approximately 25 per cent of ammo.iia
while the latter contains only about 14 per cent. Thus, the
same weight of phosphoric acid can be used to fix approxi-
mately twice the quantity of ammonia in the production of
diammonium phosphate as, in the formation of the mono-
phosphate and a corresponding economy is effected in manu-
facturing cost per unit of plant food. The importance of
this is reflected in the increasing quantity of diammonium
phosphate now being produced for fertilizer purposes.
The preparation of triammonium phosphate as a step in
the manufacture of the mono- and di-ammonium compounds
was first proposed by Cameron,9 of the Bureau of Soils. The
process was recommended particularly for the recovery of
phosphoric acid from solutions of low concentration. It con-
sists in passing ammonia gas into the phosphoric acid solution
in a closed vessel until a pressure of 1 to 5 pounds is developed.
The phosphoric acid is thereby precipitated as the triphos-
phate. The precipitated salt is separated from the mother
liquor and gently heated to convert it into the mono- or di-
ammonium phosphate or a mixture of these salts. The am-
monia evolved in this treatment, as well as that given off on
heating the mother liquor with the addition of lime, is re-
covered for use again in the process.
The procedure of forming triammonium phosphate as a
step in the preparation of the mono and di compounds is also
applied in a process that has recently'been proposed by Lloyd
and Kennedy.10 The method involves the use of ammonium
acid sulfate as-a cyclic carrier for the phosphate content of
phosphate rock. The steps in the process are as follows:
(1) Ground phosphate rock is digested with a strong solution
of ammonium acid sulfate to .give a solution containing am-
monium sulfate and phosphoric acid, together with a precipitate
containing calcium sulfate which is separated by filtration or
countercurrent decantation.
Ca3(P04)2 + 6NH4HSO, 3(NH4)2S04 + 2H,P04 + 3CaSO,
=
(2) An excess of ammonia is added to the filtrate to precipitate
triammonium phosphate leaving ammonium sulfate in solution.
3(NH4)2S04 + 2HsP04 + 6NHa 2(NH4)3P04 + 3(NH4)2S04
=
(3) The precipitate of triammonium phosphate is separated
from the mother liquor and heated to form diammonium phos-
phate, which is then pulverized to commercial form. The am-
monium evolved is recovered.
(4) The precipitate of calcium sulfate from (1) is digested
with ammonia and carbon dioxide to produce a precipitate of
calcium carbonate and a solution of ammonium sulfate.
3 CaS04 + 6NH3 + 3C02 + 3H20 = 3CaC03 + 3(NH4)2S04
(5) The ammonium sulfate formed in reactions (2) and (4)
is recovered by crystallization and the crystals heated to about
300° C. to produce ammonia and ammonium acid sulfate for use
again in the process.
A comparison of this method with the sulfuric acid method
of producing ammonium phosphate will show that the rela-
tive cost of the two methods depends on the relative cost of
producing free sulfuric acid and of producing it in the form
of ammonium sulfate by the German calcium sulfate method.
If the cost of producing free sulfuric acid by present methods is
considerably more than that of producing it in the form of am-
monium sulfate by the gypsum process, then the ammonium
acid sulfate method of producing ammonium phosphate may
be more economical than the present sulfuric acid method.
The reverse must prove true, however, in those localities
where the cost of producing sulfuric acid as ammonium sulfate
by the gypsum method is equal to or greater than the cost of
preparing free sulfuric acid.
«
Cameron, U. S. Patent 1,276,870 (1918).
10
Lloyd and Kennedy, Mfrs. Record, 92, No. 26, 53 (1927).
March, 1929 INDUSTRIAL AND ENGINEERING CHEMISTRY 289

A study has been made in this11 and other laboratories of
the possibility of converting volatilized phosphoric acid into
ammonium phosphate directly by passing ammonia gas into
the treater in which phosphoric acid is precipitated. It has
been found difficult, however, to control the addition of the
ammonia to the system so as to give a product of the desired
composition, and the method apparently offers no advantage
n Ross, Merz, and Carothers, U, 3. Patent 1,194,077 (1916);
Ross, and Carothers, U, S. Patent 1,284,200 (1918).
over the procedure of collecting the acid and treating it with
ammonia in separate operations.
Considerable attention has also been given to the direct
preparation of ammonium phosphate from phosphate rock by
digesting with ammonium salts such as the sulfate and car-
bonate under pressure.12 Some soluble phosphate is formed
under these conditions, but the percentage recovery is too
small to offer much promise of commercial application.
Merz, 15
Muckenberger, Z. anorg. allgem. Ckem„ Í69, 81 (1928); Blamenberg,
U. S. Patent 1,638,677 (1928).

Dissection of Wood Fibrils by Chemical Means1

George J. Ritter
U. S. Forest Products Laboratory, Madison, Wig,

A previous paper2 it was reported that fibers in hard- fied spruce and elm fibers were treated with 68 to 77 per cent
woods and traeheids in softwoods are composed of layers,
IN and that these layers are composed of fibrils. As a part
phosphoric acid at a
temperature of 60°
of the experimentation reported in that paper, the layers to 65° C. for 15
and then the fibrils were separated by chemical means, in to 20 minutes and
order to obtain the building units of the microstrueture of then were examined
the fibers by dissection in natural planes of cleavage. with the aid of a
Since the manuscript of the earlier paper was sent to the microscope. In a
publisher, it has been discovered that the fibrils themselves large proportion of
are in turn composed of tiny, natural building units and that the fibers the fibrils
these units can be separated by chemical means. had begun to sepa-
The tiny units of which a fibril is composed are spindle- rate into the spindle-
like in shape. They are arranged normally with their pointed like bodies that ap-
ends overlapping slightly, thus forming a single, slender, pear to be the small-
threadlike structure (fibril) of a diameter approximately est building units of
uniform throughout its entire length. It is not definitely the fibrils visible
known whether the units are held together by a cementing with the high power
material that acts similarly to the lignin between the wood of the-microscope.
fibers, but judging by the conditions required to separate The conditions (con-
the units, it does seem probable that such a material is present. centration of acid,
In the experimentation now under consideration deligni- temperature, and
1Presented before the Division of Cellulose Chemistry at the 76th time) under which
Meeting of the American Chemical Society, Swampscott, Mass., September the fibrils of the two
10 to 14, 1928. species separated Plate III—Separation of Cell-Wall
*
Ritter, Ind. Eng. Chem., 20, 941 (1928). into the smaller Layers into Fibrils More Nearly Com-
plete than That of Plate II, 800 X

Plate I—Threadlike Structured in

Middle Portion of Oblique Fiber Shows Plate II—Yarnlike Appearance of a Plate IV—“Fusiform Bodies11 into
Fibrils Layer Partly Loosened
of Inner Fiber after Fibrils Have Been Well Which Fibrils Have Been Separated.
by Phosphoric Add Treatment. 800 X Loosened. 800 X 1000 X