Published September, 1959
Nature of the Reactions of Monocalcium Phosphate Monohydrate in Soils:
III. Studies With Metastable Triple­Point Solution1
W. L. LINDSAY, J. R. LEHR, AND H. F. SxEPHENSON2
ABSTRACT
Metastable triple­point solution (MTPS), the solution
saturated with respect to Ca(H2PO4)2vH2O and CaHPO4­
2H2O, was reacted with a series of soil samples in order to
simulate the initial reaction zone that occurs adjacent to
a dissolving granule of superphosphate in soil.
As this acidic solution (initially pH 1.48) contacted suc­
cessive soil increments, appreciable quantities of AI, Fe,
Mn, K, and Ca were dissolved or exchanged from the soil.
The solution formed during this series of reactions gradu­
ally became supersaturated with respect to certain Ca and
Fe­Al phosphate compounds. As the pH rose above 2.3,
more rapid precipitation of phosphates occurred and was
accompanied by the simultaneous removal of Ca, Al, Fe,
and K from solution. The crystalline compound, CaHPO4­
2H2O, CaHPO4, and H8K3AiB(PO4)8­18H2O, were identi­
fied petrographically and by X­ray as precipitates that
later formed in solutions filtered during the reaction se­
quence. The results are compared to those of a previous
study in which soil was reacted with TPS (the stable equi­
librium solution saturated with respect to Ca(HoPO4)9'H.,O
and CaHPOJ.
A s SHOWN in an earlier paper of this series (3),
Ca(H2PO4)2­H2O (MCP) dissolves in soils to produce
an acidic reaction zone in which appreciable quantities of
Fe, Al, Mn, and other soil constituents are dissolved. The
chemical environment that may be expected to occur
within such a soil­fertilizer reaction zone was simulated
in a second study (4) by reacting TPS (stable triple­point
solution saturated with respect to Ca(H2PO4)2'H2O and
the stable hydrolysis product CaHPO4) with successive
samples of soil. This latter study provided evidence that
the Fe, Al, and Ca dissolved from the soil was later pre­
cipitated along with some of the fertilizer P. It was recog­
nized from these and previous studies (1, 2) that the
metastable CaHPO4­2H2O is likely a more important ini­
tial hydrolysis product from Ca(H2PO4)2­H2O in soils than
is the stable but more slowly formed CaHPO4.
The objective of the present study was to investigate
the reactions that take place between soil and MTPS
(solution saturated with respect to Ca(H,PO4)2­H,O and
the metastable hydrolysis product CaHPO4­2H2O). The
 LINDSAY ET AL.: REACTIONS OF MONOCALCIUM PHOSPHATE MONOHYDRATE IN SOILS: STUDIES WITH MTPS 343

I 2 3 4 5 6 7 8 9 10 O 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
NUMBER OF SOIL INCREMENTS CONTACTED NUMBER OF SOIL INCREMENTS CONTACTED NUMBER OF SOIL INCREMENTS CONTACTED

I 2 3 4 5 6 7 8 9 10 I 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 9 9
NUMBER OF SOIL INCREMENTS CONTACTED NUMBER OF SOIL INCREMENTS CONTACTED NUMBER OF SOIL INCREMENTS CONTACTED

Figure 1—Change in pH and concentration of P, Ca, Al, Fe, K, and Mn in solution during reaction of MTPS with
successive increments of soil as influenced by time of contact with each increment.
approach used was to react MTPS successively with a
series of soil samples in order to simulate the chemical
environment in soil near a dissolving granule of MCP.
The basis for this scheme was developed previously (4).
Even though the compositions of the two triple­point solu­
tions differ very little, the pH difference (1.48 for MTPS
compared to 1.01 for TPS) may be important. A further
objective was to examine more critically the sequence of
precipitations that may be expected to occur in the soil­
MCP reaction zone.
MATERIALS AND METHODS
Preparation of MTPS.—Because MTPS is supersaturated
with respect to CaHPO4, it is metastable and must, therefore,
be prepared just prior to use. For its preparation, 600 g. of
reagent­grade Ca(H 2 PO4)2­H 2 O and1 600 g. of water were stirred
together at 25° C. for periods from 2 to 24 hours. The suspen­
sion was filtered and its composition determined by methods
given previously ( 3 ) . In all cases, its chemical composition
checked with that of MTPS (3) which is 1.44M Ca, 3.98M P,
with a density of 1.284 and a pH of 1.48.
Soils med.— The slightly calcareous Rosebud loam (pH 7.6,
from Nebraska) was used in this study. The HCl­soluble Fe,
Al, Mn, Ca, and P of this soil were reported earlier ( 4 ) .
Samples of the air­dried soil were sieved through a 16­mesh
screen and sufficient water was added to bring the soil to
exactly 5% moisture (based on oven­dry weight at 110° C.)!
Reaction of MTPS with successive increments of soil.—To
400 g. of soil (oven­dry basis) containing 5% moisture, 800 ml.
of MTPS was added. The suspension was shaken for 1 hour
on a mechanical shaker and filtered in a pressure cell through
S and S Blue Ribbon filter paper. A 20­ml. aliquot of clear
filtrate was removed for chemical analysis and the remainder
was added to a second sample of soil of such mass that the
ratio of soil (g.) to filtrate (ml.) was always 1:2. This reaction
sequence was repeated with successive soil increments until
no filtrate remained for further reactions.
A second series of reactions was carried out in a similar
manner except that the shaking time for each suspension was
5 hours instead of 1 hour.
Analyses of filtrates and precipitates.—A 10­ml. aliquot of
each of the filtrates was digested with HNO3 and HC1O4, and
chemical determinations were made for Ca, P, Fe, Al, and Mn,
as previously described (3). The concentration of K was deter­
mined with the Beckman DU spectrophotometer after first
adjusting to fixed levels the concentrations of Ca, HC1O4, and P,
in all standards and unknowns.
The pH was determined in each filtrate with the Beckman
Model G pH meter, immediately after filtration. A second
10­ml. aliquot of each filtrate was stoppered in a flask and
allowed to remain quiescent. The pH was determined on these
filtrates at 5 weeks and 6 months. Solids that had precipitated
from solution at 1, 5, and 9 weeks were examined petrograph­
ically and by X­ray by removing a portion of the precipitates
and washing it first with water and finally with acetone.
RESULTS AND DISCUSSION
In this study MTPS was reacted successively with 10
increments of Rosebud loam. Changes in the chemical
composition of solution that resulted from each of these
reactions are shown in figure 1. The precipitates that later
formed in a separate portion of each of these solutions are
344 SOIL SCIENCE SOCIETY PROCEEDINGS 1959

described briefly in table 1. The present reaction scheme CaCO3 equivalent, hence its reaction with MTPS is ex­
was used as a means of simulating the chemical processes pected to increase Ca in solution, as shown by the "no
that can occur in the vicinity of a dissolving MCP granule precipitation" Ca line in figure 1. This line was calculated
as MTPS, formed within the granule, moves outward into on the basis that 76 mmols. Ca dissolved from each 500 g.
the surrounding soil. of soil (4), that no Ca reprecipitated, and that dilution was
The curves in figure 1 reveal that appreciable quantities directly proportional to the 5% moisture in the soil. Since
of Al, Fe, K, Mn, and Ca, were dissolved from this soil the Ca concentration remained nearly constant during re­
by reaction with MTPS. These reactions were accompa­ action with the first 5 or 6 soil increments, it may be con­
nied by a gradual increase in pH from that of the original cluded that Ca disolved from the soil caused supersatura­
fertilizer solution (pH 1.48). The broken lines in this figure tion with respect to CaHPO4'2H2O, which resulted in
indicate that only a small fraction of the total HCl­soluble partial precipitation of the added Ca.
Fe and Al of Rosebud soil (4) was actually dissolved Precipitation of CaHPO4­2H2O started during the
during the reactions with MTPS. Increasing the time of 1­hour contact of solution with each soil increment and
contact of the fertilizer solution with each soil increment continued later in the filtered solution, as evidenced by
from 1 to 5 hours caused both the dissolution and precipi­ the consistent presence of crystalline CaHPCy2H2O in
tation to proceed more extensively. During contact with the filtrates at the time of the 1­week examination period
the initial soil increments, the concentrations of dissolved (table 1). Increasing the reaction time with each soil incre­
soil components increased as the solution contacted suc­ ment to 5 hours enabled most of the precipitable CaHPO4­
ceeding increments due to the fact that components dis­ 2H2O to form while in contact with the soil prior to filtra­
solved from one increment of soil were added to those tion, so that at the 1­week examination period only minor
dissolved from previous ones. During reaction with the amounts remained to precipitate in the filtrates.
latter soil increments (seventh through tenth), the concen­ As the concentration of Fe and Al increased in solution
trations of cations leveled off and later decreased. This during the sequence of reactions of the present study, the
leveling off or decrease in cation concentration may be solutions became supersaturated with respect to certain
accounted for largely by reprecipitation reactions which phosphate compounds which contained K, Fe, Al, or Ca.
occurred as the solubility of various phosphates and oxides This is particularly evident from solutions contacting five
were exceeded and by a reduced dissolution rate of the or more soil increments. Increasing reaction time resulted
soil bases as the pH of the medium gradually increased. in more extensive precipitation, especially from solutions
The slight dilution effect due to moisture present in the that had reacted with the greater number of soil incre­
soil likely played a minor role. ments. The only crystalline compound, in addition to the
The formation of precipitates in all of the solutions re­ dicalcium phosphates, that was subsequently identified
sulting from reaction of MTPS with soil (table 1) indicates in the filtrates, was the potassium aluminum taranakite,
that the solution was always supersaturated with respect H6K3A15(PO4)8'18H2O. This compound has been described
to various phosphate compounds. The original MTPS, by Smith and Brown (6). This complex phosphate salt
although saturated with respect to Ca(H2PO4)2'H2O was fairly abundant at the time of the 5­week examination,
and CaHPO4'2H2O, was supersaturated with respect to but was even more abundant at 9 weeks.
CaHPO4. This salt generally crystallized very slowly. The There was another precipitated material present in the
Rosebud soil used here contained approximately 1.5% form of colloidal amorphous solids which could not be
Table 1—Petrographic and X-ray identification of crystalline solids that precipitated from solution subsequent to the
reaction of MTPS with Rosebud soil.
Reaction time No. of soil After 1 week After 5 weeks After 9 weeks
of solution increments Solid Abundance* Solid Abundance* Solid Abundance*
with soil reacted
1 hour t Ca(H2PO,)2.H20 + CaHPO, ++ CaHPO, +
*
CaHPO, • 2H2 O + CaHPOj • 2H2 O
2 CaHPO, • 2H2 0 + CaHPO, • 2H2 0 ++ CaHPO, > 2H2 O ­H­
CaHPO, T CaHPO, T
3 CaHPO, • 2H 2 O + CaHPO, • 2H2 O ­H­ CaHPO, • 2H2 O ­H­
CaHPO, T
4 CaHPO, • 2H 2 O + CaHPO, • 2H2 O ++ CaHPO, • 2Hj O +++
5 CaHPO, • 2H 2 0 t CaHPO, • 2H, O ­H­ CaHPO, • 2H2 0 ­H­
6 CaHPO, • 2H, O ++ CaHPO, • 2H 2 O 4­+ CaHPO, • 2H2 O ++
CaHPO, T CaHPO, T
7 CaHPO,­2H,O + CaHPO, • 2H2 O H­ CaHPO, • 2H2 O
T
8 CaHPO, • 2H 2 0 + CaHPO, ­ 2 H j O 1­+ CaHPO, • 2H 2 O
H,k 3 Alj(PO,),­18H 2 0 + H S K $ A1 S (PO,),­18H 2 0 T
CaHPO, 2H, O + CaHPO, • 2H; O ++ CaHPO, • 2H2 O ­H­
' H,K,A1 S (PO,),­18H 2 0 + H.KjAlsfPOjB­lSHjO
5 hours 0 CaHPO, 2H 2 O +
CaHPO, T CaHPO, + CaHPO, ^­f
1 No No CaHPO, • 2H2 O T
2 No CaHPO, • 2H 2 O T CaHPO, 2H2 O +
3 CaHPO, ­ 2 H 2 O + CaHPO, • 2H 2 O ++ CaHPO, • 2H2 O • H­
4 No CaHPO, • 2H2 0 + CaHPO, • 2H2 O ++
S No CaHPO, ­2H;O ­H­ CaHPO, • 2H, O +
*

6 CaHPO, • 2H2 O + CaHPO, • 2H2 O ++ CaHPO, • 2H2 0 ­H­

H ( KjAl s (PO,),­18H 2 O + H,K3A1, (PO,),­18H 2 0
(Amorphous Fe­P phase) T
7 CaHPO, • 2H2 O + CaHPO, • 2H2 O ++ CaHPO, • 2H2 O • H­
• H­
< ! !
CaHPO,* T
. 8 H,KjAl5(PO,),­18H 2 0 + H,KjAl s (PO,),'18H 2 O ++ HjK,Al s (PO,),­18H 2 O ­H­
CaHPO, • 2H2 O + CaHPO, • 2H 2 O • H­

* T = trace precipitate; + = light precipitate; ­H­ = medium precipitate; • *• ++ = heavy precipitate.

 LINDSAY ET AL.: REACTIONS OF MONOCALCIUM PHOSPHATE MONOHYDRATE IN SOILS: STUDIES WITH MTPS 345

identified by either petrographic or X­ray methods, but Table 2—Changes in pH of filtrates subsequent to the reac­
which contained Fe and P, as indicated by microchemical tion of MTPS with various increments of Rosebud
tests. The solids, in this case, were well suited for petro­ soil (1­hour reaction series).
graphic and X­ray examinations for the detection of crys­
talline Fe phosphate species had they been present. The No of PH
concentration of Fe in solution was about one­fourth that soil increments
contacted Initially After 5 weeks After 6 months
of Al, as shown in figure 1, and the possibility that small 0 1.48 _ 1.29
amounts of Fe may have substituted for Al in the tarana­ 1 1.65 1.61 1. 33
kite cannot be eliminated. 2
3
1 83
1.89 80
75 1.69
1 76
One significant observation is that the amount of 4 1. 96 88 1 85
5 2.07
CaHPO4'2H2O precipitated from the filtrates increased 6 2.21
94
98
1. 89
1. 91
with time, particularly from those solutions in which crys­ 7 2.35 2 06 1.93
talline taranakite and the colloidal iron phosphate precipi­ 8 2.47 2 07 1.91
9 2.53 2 07 1.96
tates were most plentiful. As pointed out by Brown and 10 2.49 ­ ­
Lehr (1), the precipitation of P by cations other than Ca
would be expected to cause supersaturation with respect to
either of the dicalcium phosphates and consequently a was only about one­tenth that dissolved by TPS. This
further precipitation of P as CaHPO4­2H2O or CaHPO4 difference can likely be explained by the much lower rate
would be predicted. of solution of the iron oxides of the soil at pH 1.48 of
The CaHPO4­2H2O present after 1 week in solutions MTPS as compared to that at pH 1.01 of TPS. The second
obtained with the 1­hour extractions was in the form of difference is that with TPS there was found crystalline
either coarse spherulitic aggregates or massive crusts of H8K(Fe,Al)3(PO4)e­6H2O (oxide ratio 1:3:6:20), but this
intergrown crystallites, indicating that precipitation ini­ salt was not detected in the present study, possibly due
tially was very rapid. With time, as the rate of pre­ to the lower concentrations of Fe. Only one of the fil­
cipitation diminished, the newly formed CaHPO4­2H2O trates from the previous study with TPS (4) precipitated
crystallized as better­formed monocrystals of acicular and taranakite.
needle­like habits. The precipitation of CaHPO4 occurred The extent of dissolution of Al from soil by MTPS was
most extensively in the more acid filtrates which had con­ nearly the same as with TPS, indicating that the dissolu­
tacted only 1 or 2 soil increments. These observations indi­ tion rate of Al was not affected very much by the change
cate that the formation of the metastable CaHPO4­2H2O from pH 1.01 to 1.48. The dissolution of Mn was also
was favored over that of CaHPO4, and, further, that the nearly identical in the two studies. There were no indica­
transformation of the metastable dihydrate to more stable tions that Mn was involved in the precipitation reactions
anhydrous dicalcium phosphate was very slow at pH at the pH ranges encountered in either study.
values far above that of MTPS. These results provide CONCLUSIONS
further evidence that the dihydrate is very likely a more
important initial reaction product in soils than is the an­ The present study further suggests the importance of
hydrous form. CaHPO4­2H2O as an initial soil­fertilizer reaction product
Changes of pH in the filtrates from the 1­hour reaction in the vicinity of MCP granules in soils. Its importance
series over a 6­month period following the initial reaction is expected to increase as the Ca content of the soil is
of soil and MTPS are shown in table 2. In all cases the increased, as in the more highly calcareous soils.
pH decreased with time, reflecting the release of H+ as Much of the fertilizer P from MCP is likely precipitated
the more basic precipitates slowly formed. The rather initially in the pH range 2.3 to 3.0. It appears that Al
large decrease in pH of the original MTPS and of the fil­ plays a secondary role and Fe a tertiary role in the initial
trate following reaction with the first increment of soil reactions between soil and fertilizer P from MCP. It would
reflects the precipitation of CaHPO4 (table 1) with the further appear that H6K3Alg(PO4)8­18H2O is one of the
release of additional H+. Since CaHPO4 precipitation was initial reaction products. Another consideration that has
not extensive in the filtrates from subsequent soil incre­ been largely neglected is that soil K is involved in the
ments (table 1), the corresponding decreases in pH were dissolution and subsequent precipitation reactions expected
less. Beyond tie fifth soil increment, the decrease in pH in the vicinity of placements of superphosphates. This
upon standing was again more pronounced, reflecting the interesting chemical effect should be investigated. Some of
formation of more basic Fe and Al phosphates and the the implications of the present study are discussed further
more abundant precipitation of CaHPO4­2H2O. Flatten­ in a companion paper of this series (5).
ing of the pH curves in figure 1 also reflects the release
of H+ during the precipitation reactions which involved
Al, Fe, Ca, K, and P. It would appear that the more
abundant precipitation of the fertilizer phosphorus, as the
pH approached approximately 2.3, releases additional H+
ions which did not permit the pH to rise as rapidly as
might otherwise be expected. The initial soil­MCP reac­
tion products are expected to be those which form between
pH 2.3 to 3.0. The P curve in figure 1 also shows a more
rapid precipitation of P beyond the sixth soil increment,
particularly in the 5­hour reaction series. This would indi­
cate that the precipitation reactions responsible for the
removal of P from solution takes time. Had it been pos­
sible to continue the reaction sequence to include more
soil increments, very likely the precipitation reactions
would have increased much more extensively.
A comparison of the results in the present experiment
with those of the previous study in which the same Rose­
bud soil was reacted with TPS (4) revealed two important
differences. First, the amount of Fe dissolved by MTPS