J

rolvsis o J
e J
rate
s S

W h e n sodium tripho5phdte tiyclrol: i e s , one mole each
of ortho- and pyrophosphate if formed. In aqueous solu-
tions of hexametaphosphate tFc o reaction5 take p1ace
simultaneously ; part is hydrolyr,ed directlj to ortho-
phosphate, and part is depol? meriLed to trimetaphosphate
which then hydrolgzes sloitlj to orthophosphate. 1x1 the
hydrolysiq of triniela- to orthophosphate, triphosphate is
formed as an intermediate. In the pIeseiice of an exces5
El?EIIEK:CI<Sin thr literature to the use of molecularly
dehydrated phosphates, in the treatment' of water for vari-
ous purposes, are too numerous to be tabulated here. The useful
life of these compounds is dependent on their ability to with-.
stand hydrolysis iri aqueous solutions. Many attempts ha1.c.
been made to measure the rate a t which these compounds rehy-
drate (hydrolyze), but' the analytical methods used were inad(,-
quate to establish either the nature or the exact amount of t h c b

of alkali, trimetaphosphate is coni erted entire13 t o tri- products formed. Xorgen and Swoope (8) used the titratioir
phosphate. P>rophosphates hydro1:se directly to ortho methods of Gerber and Miles (4),rThich do not determine pol).-
phosphates. Hydrolysis data confirm the fapi that tetra- phosphate as such. Germain ( 5 ) determined the hexametapho+
and septaphosphateb art' mixtures. phate by precipitating as barium hexametaphosphate and the.
pyro- and orthophosphate by acidimetric titrations using a scL-
Ties of indicators. Katzcl (10) also used titration methods. Noiic.
100;: of these methods gave sufficient, information on the produrtq
formed or the mechanics of the rehydration.
Recently developed met,hods for determining triphospharv
and pyrophosphato ( 2 ) in the presence of each other and in tht.
eo
pre%enceof the other phosphates have made possible a more coni-
plete study of the hydrolysis of the dehydrated phosphatc.5.
Supplementing t,he above methods, the orthophosphate x a s d(,-
iwmined colorimetrically by the molybdenum blue method ( 3 ,
0 60
k and the hexametaphosphate precipitated as barium hexametw-
0 phosphate ( 7 ) . S o satisfactory method was found for determiti-
2
0 40
ing trimetaphosphate in the presence of large amounts of ot1it.i.
v phosphates, and it was therefore determined by difference. l ? f b -
sulk found by analysis of pyrophosphate, polyphosphate, ailti
hexametaphosphate, using the above methods, agree with t l i c -
20 findings of Andrese and Kust (1) and Partridge, Hicks, arid
Smith .(9)-namely, t'hat only one true polyphosphate, the tri-
phosphate, exists. The so-called tetraphosphate and septaphoi-
\ I \ I I I I I phate were found to be mixtures of triphosphate and niet,apho<-
IO 20 30 40 50 phate iyith small amounts of ortho- and pyrophosphate usu:ill>-
roo; prcsmt,
HYDROLYSIS
MATERIAL^. (Table 1) Thc tetrasodium pyrophosphate used
was a commercial grade containing 53.2% P2Oj. The trisodium
80 hydrogen pyrophosphate (Ka~HP20,.H20)Ras obtained from
Monsanto Chemical Company a,nd contained 54.5% Pz05. The
disodiuni acid pyrophospha,te used was a commercial grade
containing 63.1 yoP z O ~ .
2
0 60
k
;
5 4c PnOs
Calcd.,
%
P
of 1%
Soln.
I'yrophoa phntes
Tetrasodium Crystalline X;a;PzO, 63.4 10.2
Trisodium Crystalline iYa3HPzO: 58.2 7.3
x Disodium
I'olyphosphates
Crystalline SalHzPd3i 64.0 4.8
Triphosphate Cryetiilline NabPeOia 57.9 9.4
Tetraphosphate Amorphous 3KazO-2PdJn 60.4 R O O
Septaphosphate Amorphous 4 S i a d - 3 5P20i 84.0 7 8
Metaphosphates
Hexametaphoh Amorphous SazO-PnOn 69.6 8.21.
0 IO 20 30 40 50 Hexametaphos Amorphous NazO-P%Oa 69.6 6.ac
TIME IN news rrirnetaphos Crystalline (SaPOs)a 69.6 6.7

Figure 1. Sodium Pyrophosphaies " Commercial grade containing 6 2 . 5 % P z O ~ .

h Laboratory-prepared product containing 89.6% PzOs.
c Commercia.1 grade conminine 67.25; PLh.
A . 1%solution in water at 100' C .
€2. 1 % solution in water a t 70' 6.

136
February 1947 INDUSTRIAL AND ENGINEERING CHEMISTRY

10 20 40 50
roo7 j roog: ORTHOPHO3PHATE

P Y ROFUOSPHA T E

ao 80

260
2
t
4
L

0 TRIPHOSPHATE
a
5 40
U

20 20 E

1 I 1
2 4 6 8 10 0 10 20 30 40 50
TIME IN HOURS

ORTHOPHOSPHATE

Figure 2. Sodium Triphosphate (Commercial)

A. 1 qo solution i n water a t 100' C.
B. 10% solution i n water at 100' C.
C. 1 % solution i n 1 % NaOH at 100' C.
D. 1 % solution in 1 % NaOH a t 100' C., over 60 hours
E . 1% solution in wkter at 70' C., over 60 hours

(commonly called tripolyphosphate) n-ab a commercial grade

containing 57.5% PzOP. The sodium tetraphosphate was a
commercial grade containing 62.5% P z O ~and
, the septaphosphate
was a commercial grade containing 63.5% P~OS.
METHOD.Solutions of the desired concentration (1% or 10%)

2ol 1 I
B 4
I I

6
I
8
I

IO
TIME IN HOURS
The laboratory-prepared sodium metaphosphate referred to as
hexametaphosphate was made from twice-recrystallized mono-
sodium orthophosphate by heating to 800' to 900' C. and cooling
rapidly between steel plates. All of the samples made in this
manner contained between 90 and 93Y0 of sodium heximetaphos-
phate by analysis. The balance was triphosphate. The material
used in these tests contained 69.6970 P 2 0 5 .
The commercial hexametaphosphate used was unadjusted
Calgon glass containing 67.2% PzO6. The sodium trimetaphos-
phate was a commercial grade of the water-soluble crystalline
polymer containing 69.6% P206. The sodium triphosphate
were made and aliquots removed for analysis. Ortho-, pyro-,
tri-, and hexametaphosphates were determined by the methods
described. Trimetaphosphate when present was determined by
difference. The solutions were heated to the desired temperature,
70" or 100" C., and aliquots were remoqed periodically, cooled,
and analyzed as before.
The data are presented in a new way. Inasmuch as the inter-
mediate products of the rehydration were determined, and their
presence materially affected the evaluation of the product, these
products are shown in the hydrolysis curves. In the curves
shown, the percentage of phosphorus present as ortho-,. pyro-,
tri-, hexameta-, and trimetaphosphate is plotted against time, so
that the composition of the solute can be calculated a t any given
time, The area between the curves represents the percentage of
phosphorus present as ortho-, pyro-, etc., as indicated. Thus the
figures picture not only the disappearance of the starting material
but also the formation of intermediates, a knowledge of which is
necessary in determining the useful life of the product. The ini-
tial composition of each of the products, expressed in per cent of
phosphorus, is shown a t zero time.
138 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 39, No. 2

loo?

80
ORTHOPHOSPHATE

2 60
F"5
0
240 TRLMETAPHOSPHATE
8 - 1 H E X AMETAPHOSPHATE

20
A TP IM E T A PHOSPUATE

I I I I I 1 I

IO 20 30 40 Y) 4 6 8 IO

100 % 100,".

ORTHOPUOSPHATE

80

I \ TRIPHOSPHATE

0
I
z 4
TRIPHOSPHATE

I I
6
I
0
I
IO
B
I
2ot \ HEXAMETAP O S P H A T E

2 4 6 8 10
B
100%
TIME IN HOURS
Figure 3. Sodium Trimetaphosphate (Commercial)
A . 1% solution in water a t 100' C.
B . 1%solution in 1% NaOH at 100' C. 80

DISCUSSOX 0 601
i
PYROPHOSPHATES. Figure 1-4 shows the rates of hydrolysis
of 1yo solutions of tetrasodium, trisodium hydrogen, and diso-
HEXAMETAPHOSPHATE
dium acid pyrophosphates a t 100" C. in distilled water. Since
the pyrophosphates hydrolyze directly to orthophosphate, all are
-
c
shown on the same figure. The area above each curve shows the
percentage of phosphorus which has been hydrolyzed to ortho-
phosphate; that below the curve is the percentage of phosphorus
remaining as pyrophosphate. This indicates the marked effect of
lower pH on the rate of rehydration of pyrophosphates. (Table
*O t
I shows the pH of 1% solutions of the dehydrated phosphates.) I TRlMETAbHpSPHATE
The acid salt, disodium acid pyrophosphate, hydrolyzes rapidly. 0 10 20 30 40 50
The trisodium hydrogenpyrophosphate is slightly more stable, and TIME IN HOURS
the normal salt, tetrasodium pyrophosphate, is relatively stable. Figure 1. Sodium Hexametaphosphate (Laboratory)
In IT0sodium hydroxide solution no hydrolysis is detectable in A . 1 yo solution in water a t 100' C.
96 hours at 100" C. Temperature also greatly affects the rate of B. 1 % solution in 1%NaOH at 1OOo C.
C. 1%solution in water a t 70b C.
hydrolysis of the dehydrated phosphates. At 70" C. the diso-
dium acid pyrophosphate rehydrates much more slowly than at,
100' C., and the tetrasodium pyrophosphate is unchanged for 60 10% decreases the stability slightly (Figure 2B) but does not
hours (Figure 1B). materially change the shape of the curves, In 1% sodium hy-
TRIPHOSPHATES. Figure 2 shows the rate of hydrolysis of droxide solution sodium triphosphate is slightly more stable than
a commercial grade of sodium triphosphate a t 70" C. and 100" C. i n water (Figure 2C). Since pyrophosphate is found to be entirely
Khen sodium triphosphate hydrolyzes, both ortho- and pyro- stable in 1% sodium hydroxide solution a t 100" C., extending the
phosphates are formed. Increasing the concentration from 1 to curve in Figure 2C should indicate the mechanism of the hydroly-
February 1947 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 139

I\ \ ORTHOPHOSPHATE
A
ORTHOPHOSPHATE
C

PYROPHOSPHATE

"t/
TRIPHOSPHATE
20
TRIMETAPHOSPHATE

I 1 I
2 4 6 8 IO 2 4 6 8 10
100
7-1
ORTHOPHOSPHATE
B
80 -
ORTHOPHOSPHATE

TR IPHOSWATE

PYROPHOSPHATE
R
8
t
840 - HEXAMETAPHOSPHATE

TRIMETAPHOSPHATE z0 10 20 40
30 TRIMETAPHOSPHATE
50 o
I I I I
0 2 4 6 8 10
T I M E IN HOURS TIME IN HOURS
Figure 5. Sodium Hexametaphosphate (Commercial)
A . 1 c/o solution in water at 100' C. C . 1 % solution in 1 % NaOH at 100' C.
B . 10% solution i n water at 100° C . D . 1 % solution in water at 70' C.

sis of triphosphate. Figure 2 0 shows triphosphate in 1% sodium hexametaphosphates will supplement the triphosphate discussion
hydroxide solution plotted over 60 hours. The ratio of phosphorus above and provide a basis for evaluating the results found on the
present as orthophosphate to that present as pyrophosphate mixtures. Although neither the commercial trimetaphosphate
is approximately 1to 2 a t the end of 60 hours, which means that nor the laboratory-prepared hexametaphosphate were strictly
one mole each of ortho- and pyrophosphate is formed as the result pure, the amount of impurity was not sufficient to mask their
of the hydrolysis of triphosphate (Table 11, D). At 70" C. tri- hydrolysis characteristics.
phosphate is much more stable; 80% of the phosphorus is still A 1% solution of trimetaphosphate a t 100' C. hydrolyzes
present as triphosphate after 60 hours (Figure 2B). slowly to orthophosphate (Figure 3A). However, the hydrolysis
METAPHOSPHATES. Since septaphosphate, tetraphosphate, and is not direct but appears to form triphosphate as an intermediate
the commercial hexametaphosphate were found to be mixtures product (Table 11, B and C). In 1% sodium hydroxide solution
of metaphosphate and triphosphate, and trimetaphosphate was a t 100" C. trimetaphosphate is converted immediately to triphos-
produced in the process of hydrolysis, a discussion of tri- and phate (6) and then hydrolyzes a t the rate of triphosphate in 1%
sodium hydroxide solution (Table 11,H). Comparison of Figures
3B with 2C shows this.
TABLE
11. HYDROLYSIS
EQUATIONS When a solution of the laboratory-prepared hexametaphosphate
IN WATER
is heated a t 100" C., two reactions take place. Part of the hexa-
metaphosphate is hydrolyzed to orthophosphate and part is de-
Hexametaphosphate: 3(KaPOa)a +12Hz0+2(NaPO3)3 +
12NaHzPOd (A) polymerized to trimetaphosphate. Figures 4A and 4C show that
+
-
Trimetaphosphate: (NaP03)3 H z 0 -+ NasHnPaO~o (B)
NasHzPsOm +
2Hz0 3NaHzPOd
-f (0 approximately twice as much phosphorus is hydrolyzed as is de-
Triphosphate: NarPaOlo +HzO NaaHPzOr +
NalHP04 (D) polymerized. The trimetaphosphate is determined by difference.
Pyrophosphates: NazHlPnOr +HzO + 2NaH2P01 (E) Evidence that this difference is trimetaphosphate is found by
NasHPeOi
NarPzOr ++ HzO NazHPO4
HzO + 2NaaHPOd
NaHzPOd+ (F)
(G)
comparing Figures 4A and 4B. Trimetaphosphate in 1% sodium
hydroxide was found to convert immediately to triphosphate.
IN1% NaOH SOLUTION When hexametaphosphate is hydrolyzed in a 1% sodium hydrox-
Trimetaphosphate: (NaP0a)a + Zh-aOH 4 NasPaOlo + He0 (HI ide solution a t 100" C., a large amount of triphosphate is found;
this leaves no difference to be calculated to tr:metaphosphate.
 INDUSTRIAL AND ENGINEERING CHEMISTRY
ORTHOPHOSPHATE
The identification of t,he undet>erininedmaterial as trimetaphos-
phate is based on the following points: first, its reaction with
excess alkali to form triphosphate (Figures 4-4 and 4B); second,
its rate of hydrolysis as shown by the slope of the curves after
the hexametaphosphate has disappeared (4.4 and 3 A ) ; finally
its similarity to trimetaphosphate in forming triphosphate as
an intermediate step in the hydrolysis to Orthophosphate.
Triphosphate is relatively stablc in 1% sodium hydroxide solu-
tion, and pyrophosphate is entirely stable for the time of the test.
Any triphosphate formed, therefore, should hydrolyze slowly to
ortho- and pyrophosphat'es, both of which are stable. If hesa-
metaphosphate hydrolyzes as trimetaphosphate does, by first,
forming triphosphate, the rate of formation of orthophosphate
should be the same as for triphosphate in 1%sodium hydroxide
solution (Figure 2C). Comparison shows that this js not truc.
Considerably more orthophosphate is formed during the period
ahile hexametaphosphat,e is present, (approximately 4 hours) ;
then the curve levels off to a slope corresponding to the hydrolysis
rate for triphosphate. No pyrophosphate is found a t the end of
2 hours, and only a small amount is present after 4 hours. This
latter is formed as the result of the hydrolysis of the triphos-
phate. From these observations it is evident that the portion of
hexametaphosphate n-hich hydrolyzes goes directly to orthophos-
phate. The t'riphosphate is formed from that part which depoly-
merizes to trimetaphosphate; in the presence of excess alkali the
latter converts to t,riphosphate. From t,he ratio of depolymerized
to hydrolyzed phosphorus Eqmtion A, Table 11, is believed to
represent the hydrolysis of hexametaphosphate in water.
Commercial sodium hexametaphosphate contains approxi-
mately 30% of triphosphate and 70% hexametaphosphate. The
analysis is shown a t zero time in Figure 5A, which indicates the
rate of hydrolysis of a 1%' solution of commercial hexametaphos-
phate in water a t 100" C. Hexametaphosphate is slightly less
stable in 10% than in 1% concentration (Figure 3 3 ) . Otherwise
the curves are the same.
Figure 5C presents the hydrolysis of a 1% solution of hexa-
metaphosphate in 1% sodium hydroxide solution a t 100' C. As
would be expected, a large amount of triphosphate is found, but
no trimetaphosphate. The curves are similar to those found for
the laboratory-prepared product in excess alkali. At 70" C. a
1% solution of commercial hexametaphosphate hydrolyzes as
shown (Figure 3)).As was the case with the laboratory-prepared
product, the commercial hexametaphosphate is much more stable
at 70" than a t 100" C.
POLYPHOSPHATES. Figure 6 A shows the hydrolysis of a 1%
solut,ion of com'mercial tetraphosphate in water a t 100" C. I t
Voi. 39, No. 2
ORTHOPHOSPHATE
hydrolyzes in the manner expected of such a mixture. Proof of
the existence of trimetaphosphate in this product was found by
hydrolyzing it-in a 1% sodium hydroxide solution. At the end of
2 hours a t 100' C. an increased amount of triphosphate was
found, no hexametaphosphate was present, and the analysis lcft
no difference to be calculated to trimetaphosphate. Scptaphos-
phate as shown a t zero time in Figure 6B Tvas found to be a mix-
ture of about equal quantities of hexametaphosphate and tri-
phosphate. A 1% solution a t 100" C. hydrolyzes as indicated on
the curve.
CO;YCLUSIONS
Temperature greatly affected the rate of hydrolysis of the mo-
lecularly dehydrated phosphates. The hydrolysis rates were
much slower a t 70" than a t 100" C. Triphosphate hydrolyzed
more slovly t'han hexametaphosphate and was noticeably more
stable in the presence of excess alkali.
TThen triphosphate hydrolyzed, one mole each of ortho- and
pyrophosphate was formed. Hexamet'aphosphate hydrolyzed to
orthophosphate and depoIymerized to trimetaphosphate in
aqueous solutions. The reactions were simultaneous. KOpyro-
or triphosphate was formed directly from the hydrolysis of the
hexametaphosphate. Some triphosphate was found as a result
of the hydrolysis of the trimetaphosphate formed. Trimetaphos-
phate hydrolyzed first to an acid triphosphate which then hy-
drolyzed to orthophosphate. If any pyrophosphate was formed
it was hydrolyzed to orthophosphate and the amount present
was not sufficient to be detected. I n the presence of an excess of
alkali, trimetaphosphate was converted to triphosphate, the
reaction being very rapid at 100" C.
ACKNOWLEDGMENT
The author wishes to thank Howard Adler and \V. H. Wood-
stjock for many helpful suggestions and criticism.
LITERATURE CITED
(1) Andress, K. R., and Wust, K. Z., anorg. allgem. Chem., 237,
113-21 (1938).
ENG.CHEM.,
( 2 ) Bell, R. N., IND. ANAL.ED.,in press.
(3) Fiske, C . H., and Subbarow, Y., J . Bid. Chem., 66,375 (1925).
(4) Gerber, A. B., and Miles, F. T., IXD.ENG.CHEX.,ANAL.En.,
IO,519 (1938).
(5) Germain, Louis, Chimie & industrie, 35,22-6 (1936).
(6) Hatch, G. B., U. S. Patent 2,365,190 (Dec. 19, 1944).
(7) Jones, L. T., IND.ENG.CHEM., ANAL.ED.,14, 536 (1942).
(8) Morgen, R. A., and Swoope, R. L., IND. EKG.CHEM.,35, 821-4
(1943).
(9) Partridge, E. P., Hicks, Victor, and Smith, G. W., J . Am. Chem.,
SOC.,63,454-66 (1941).
(10) Watzel, R., Die Chemie, 55, 356-9 (1942).
PRESENTED before the Division of Physical and Inorganic Chemistry a t the
109th Meeting of the A M E R I C A S CHEMICAL SOCIETY, Atlantic City, N. J.