War. Res.Vol.24,No. 12,pp. 1519-1526,1990 0043-1354/90$3.00+ 0.

00
Printed in Great Britain.All rights reserved Copyright ~ 1990 Pergamon Press pk

CHEMICAL ASPECTS OF C O A G U L A T I O N USING

A L U M I N U M SALTS I. H Y D R O L Y T I C REACTIONS
OF ALUM A N D P O L Y A L U M I N U M C H L O R I D E
Jow~ E. VAN BENSCHOTENI ~ and JAMES K. EDZWALD20
'Department of Civil Engineering, State University of New York at Buffalo, Buffalo, NY 14260 and
2Department of Civil Engineering, University of Massachusetts, Amherst, MA 01003, U.S.A.

(First receired June 1989; accepted in revisedform May 1990)

Abstract--This is the first of a two-part series of papers investigating the chemistry of AI coagulants. This
paper examines hydrolysis reactions of alum and polyaluminum chloride (PACI). Part II of the series
addresses the coagulation of fulvic acid by these coagulants.
Monomeric, polymeric and precipitated AI were identified based on a timed spectrophotometric
analysis. At typical AI doses used in water treatment, alum showed no evidence of polymer formation.
PACi consists of preformed polymers which are stable upon dilution below pH 6 and over the time frames
encountered in water treatment. Solubility studies showed that alum and PACI precipitate to form
different solid phases. Alum precipitates are adequately described by amorphous AI(OH)3(s) solubility.
The polymeric structure of PAC! is retained upon precipitation yielding a solid phase with different light
scattering characteristics, electrophoretic mobility and solubility than alum floc. AI hydrolysis is
interpreted as a coordination reaction between AI and OH-. Effects of low temperature on alum are shown
to be a result of changes in OH- caused, in part, by the temperature dependence of the ion product of
water. Hydrolysis products in PACI are preformed and therefore less sensitive to/n situ hydrolysis than
alum. Results suggest that when using alum, some of the adverse effects of low temperatures may be
mitigated by an increase in pH, thereby maintaining a constant concentration of the complexing ligand,
OH-.

Key words--coagulation, hydrolysis, alum, polyaluminum chloride

INTRODUCTION is referred to as charge neutralization or, in the case

Aluminum salts are extremely versatile coagulants
in the treatment of potable water. Using AI based
coagulants, waters of widely differing chemical
characteristics and biological quality can be success-
fully treated. Alum [AI2(SO4)3.'nH20] is the most
widely used coagulant in the water treatment indus=
try. Alum is also extensively used in both industrial
and municipal wastewater treatment. In recent years,
polymerized forms of AI have been used increasingly
in water treatment. Polyaluminum chloride (PACI) is
most common in this regard, although polyaluminum
sulfates have also been investigated.
The aqueous chemistry of A1 is complex and
upon addition of an AI coagulant in water treat=
ment, multiple reaction pathways are possible. F o r
example, coordination between AI and inorganic
ligands (e.g. PO~-, F - , O H - , SO~-) and organic
ligands (e.g. humic materials) can occur as parallel
competitive reactions. In addition, serial formation of
A! monomers, A1 polymers and AI(OH)3(s) may take
place, depending on pH. Coagulation occurs by
interaction of A1 hydrolysis products with contami-
nants such as dissolved natural organic matter and
colloidal inorganic or organic particles. The mech-
anism by which AI functions depends on which AI
species react to remove dissolved or colloidal con-
taminants. Destabilization involving AI monomers
1519
of dissolved organic substances, charge neutral-
ization/precipitation (Edzwald, 1986; Hundt and
O'Melia, 1988). Coagulation of colloidal particles in
the presence of Al(OH)s(s ) is termed enmeshment or
sweep floe. Dissolved organics can be removed by
adsorption on Al precipitates.
Insights to the chemical aspects of coagulation can
be gained by an examination of the hydrolysis of Al.
Studies of the hydrolytic reactions of AI have been
used extensively to explain coagulation mechanisms
of humic substances (Hundt and O'Melia, 1988;
Dempsey et al., 1984; Edwards and Amirtharajah,
1985; Mangravite et al., 1975). The AI species that are
observed at a given pH are assumed to be present in
the actual coagulation process under similar con-
ditions. Although such studies may lend insight
to coagulation mechanisms, the interpretation of
hydrolysis study results for water treatment plant
conditions is not straightforward. It is well known,
for example, that AI speciation is affected by the AI
concentration, mixing, type and concentration of
anion, and aging (Stol et aL, 1976; De Hek et al.,
1978; Bersillionet al., 1983). Not surprisingly,many
different AI species, especially polymers, have been
proposed. Even when AI hydrolysis is studied under
conditions similar to those in water treatment, there
is no guarantee that similar species exist in the
1520 Joh~ E. V^N B~NSCHOaZNand JAMESK. EDZWALD

presence of humic substances since hydrolysis and acetate. Details of the analytical procedure are given else-
W ~ (Van Bensehotetl and Edzwald, 1990b).
interactions between A1 and humic materials are The method used to characterize PACI and alum sol-
competitive reactions (Randtke, 1988). Furthermore, utions was a timed spectrophotometric procedure involving
differences in AI speciation would be expected reactions of AI with ferron (Smith, 1971). Three fractions
between preformed polymers and hydrolysis products designated AI" (monomers), AIb (polymers) and AI" (pre-
formed in situ. cipitated AI) were determined by the procedure. The PACI
solution was characterized periodically over a 1 year period
In this paper, the hydrolysis reactions of alum and using this procedure.
PACI are examined. The objectives of the paper are: Electrophoretic mobility (EPM) was measured using a
(1) to analyze and compare the hydrolytic reactions microelectrophoresis apparatus (Rank Brothers). For the
of alum and PACI; and (2) to evaluate how the cold water studies, samples were continuously chilled while
EPM was measured.
chemistry of these coagulants may impact their per- Turbidity was measured using a Hach Model 18900 Ratio
formance in water treatment. The coagulation of Turbidimeter.
humic substances by alum and PACI is addressed in
Part II of this series (Van Benschoten and Edzwald, RESULTS AND DISCUSSION
1990a).
P A C ! and alum
MATERIALS AND METHODS PACI was characterized periodically over a 1 year
period using the timed spectrophotometric method.
Materials
The time dependence of the reaction between AI and
PACI was prepared following the procedures of
Parthasarathy and Buttle (1985). A 2 I. Wagner type floccu. ferron has been described as (Smith, 1971):
iation jar was used as the titration vessel. A plexiglass top Al(t) = AI* + Alob(l -- e -~') (I)
with ports for stirrer, nitrogen tube, titrant tube, and pH
probe was fitted to the jar. An impeller mixer was used where
during the titration to provide vigorous mixing (1550 rpm).
Temperature was controlled at 25 4- 0.2°C by immersion of Al(t) = AI that has reacted with ferron at time t
the 2 i. fiocculation jar in a thermostaticallycontrolled water AI* = monomeric aluminum
bath. Titrant was added at a flow rate of about 0.2 ml/min.
AIb = AIb in solution at time 0
Nitrogen was continually bubbled through the solution to
remove inorganic carbon. k - - f i r s t order rate constant for type b AI
One liter of 0.1 M AICI3solution was titrated with 250 ml (min-I).
of 1.0 N NaOH. Reagents used in the titration were pre-
pared using deionized water made carbonate free by boiling. Using a least squares procedure, model parameters
The titration required approx. 22h to complete. The were estimated for the results of the timed spectro-
final PACI solution was 0.08 M A1 with a ligand number photometric analysis. Parameter values for the
(OH,,k~/AIT) of 2.5. The initial and final pH values were characterization results (5 occasions) are shown in
3.3 and 5.3, respectively.
The PACI solution was slightly cloudy at the end of the Table 1. The variables in the model (AI0b and k) are
titration, but cleared after a day or two. Similar results were significant at the 0.0001 level and multiple r 2 values
observed by Bersillon et aL (1980). are generally 0.99 or higher. Although some varia-
Experimental methods bility between the analyses is evident, the periodic
determinations are consistent. Polymerized AI (AIb)
The hydrolysis of alum [AI,(SO4)f 18H20] and PACI was
studied in jar test experiments. The standard procedure was accounts for about 90% of the total aluminum.
to add coagulant to a beaker (250 ml) containing deionized Monomeric species (AI') and precipitated AI (AI¢)
water which had been previously adjusted to an acidic level are small fractions of the total. The rate constants
(pH~e4) using 0.IN HCI. An AI dose of 10-3'3M in Table 1 reflect the reactivity of AIb with ferron.
(13.5 mR/l) was used for many experiments and is typical of
the required dose of AI needed to coagulate a water high in No obvious time dependence in the rate constant is
DOC. Following coagulant addition, the pH was then evident, indicating the nature of the polymers had not
adjusted with 0.1 N NaHCO3 and/or NaOH to the desired changed during the course of the study. The k values
value. The pH adjustment was made under vigorous stirring observed in this study are similar to determinations
with a magnetic stir bar. The beaker was then transferred to made by several investigators for solutions with
a six paddle stirrer (Phipps & Bird) and stirred at 100 rpm
(Z = 70s-') while coagulant addition and pH adjustment similar ligand values (Smith, 1971; Panhasarthy and
were carried out for the next sample. When the coagulant
addition steps were completed, all test solutions were mixed Table I. Summaryof PACIcharacterizationon
at 20rpm ( g = 1 0 s -~) for 30min, followed by l h of five occasions
settling. At the end of the sedimentation period, samples
were analyzed for pH, temperature, dissolved aluminum k ( x 100)
(0.22/~m membrane filters, Millipore type GS), turbidity Days* %AI' %AP %AF (rain-l)
and eloctrophoretic mobility. 8 2.1 90.1 7.7 2.8
Similar experiments were also conducted at 4°C making 52 8.2 92.0 -- 4,1
use of a thermostatically controlled water bath. 193 3.1 82.6 14.2 5,4
204 0.4 91.1 8.5 5.3
Analytical methods 326 2.8 93.8 3.4 4.2
AI was measured using a colorimetric procedure based on Mean 3,3 89.9 8.4 4.4
SD 2.9 4.3 4.4 I. I
the reaction of AI with 8-hydroxyquinoline (James et al.,
1983). The Al-quinolate complex was extracted in butyl *Days followingPACI preparation.
 Aluminum hydrolysis reactions 1521

0.30 1.05
I)H 4.21 ...o.....o
"~ 0.25 0.86 0.20

0.20 PACI. ALe

i o.16
i 0.15
C ~
0.10 ~ ~ - --AL b - o.~ '~ ~ o.12
i-
,,,t := o
< 0.05 0.14 <~ e,
t .o 0.08
I I I TAL° o.oo <
0.00 50 100 150 200 250
Timeis) 004
Fig. 1. Absorbanc¢ vs time for alum and PACI reacting with pH 7.41
ferron. Alum and PACI at 10-4.7 and 10-45 M AI, respect-
ively. AI fractions determined by timed reaction with ferron 0.00 20 40 6o 80 100 12o t 4 0 16o 16O 20o
illustrated for PACI sample. Time (rain)

Fig. 2. Absorbance vs time for PACI (10 -33 M AI) at three

Buffle, 1985). The time invariance of the reaction rate
constant has also been observed (Parthasarthy and
Buffle, 1985).
A comparison of PACI with alum using the
timed spectrophotometric procedure is shown in
Fig. 1. The concentrations of PACI and alum in these
samples were 10-4's M (0.85 mg AI/i) and 10-4.7 M
(0.54regAl/l), respectively. The large increase in
absorbance for PACI over time indicates the presence
of AI polymers. There is little change in absorbance
with time for alum, confirming that the dissolved
species are primarily monomers.
To investigate the effect of pH on the polymeric A!
species in PACI, filtered samples from PACI solutions
at three pH levels were evaluated using the timed
spectrophotometric procedure. The results are shown
in Fig. 2. At pH 4.2 and 5.9, most of the dissolved AI
is in a polymeric form, although at the latter pH some
particulate AI may have formed judging from the
lower absorbance on the plateau of the curve com-
pared to the pH 4.2 sample. At pH 7.4, most of the
AI had precipitated (see Solid phase and solubility),
and following filtration the remaining dissolved
species appear to be monomers. These results indicate
that below pH 6, the polymeric species in PACI
should be stable under water treatment conditions
and available for coagulation.
Solid phase and solubility
The timed spectrophotometric procedure ~as also
used to investigate the solid phases formed by precipi-
tation of alum and PACI. Alum and PACI solutions
were first titrated to pH 7.5 with NaOH to induce
precipitation. The precipitate in each case was then
dissolved by acidification to pH 4 and immediately
measured by the timed spectrophotometric pro-
cedure. The hypothesis in this experiment was that
if identical solid phases were formed by each coagu-
lant, then upon dissolution the dissolved species
should show identical reactivity with ferron. Further-
more, if the solid phase was a freshly precipitated
amorphous AI hydroxide, monomers would be
expected after acidification to pH 4. The results of
this experiment for alum (Fig. 3) indicate that this is
pH levels.
the case. For PACI, however, the polymeric structure
still exists upon dissolution of the PACI precipitate.
The redissolved precipitate was about 90% AI poly-
mers, the same as the PACI stock solution. Evidently,
the PACI precipitate is a coalition of polymers
where the individual polymeric subunits remain
intact, at least over a short time interval following
precipitation.
That PACI and alum form different solid phases
was supported by the results of microscopic inspec-
tion of the precipitates. The PACI precipitate often
appeared as small (<25/~m) spheres, clusters of
small spheres and even chain-like structures. Only at
high pH (>9) were particles observed that were
similar to alum flocs. Alum flocs usually appeared as
fluffy, porous structures, ranging in size from 25 to
100/~m. These results are in basic agreement with
recent studies which have shown that for short aging
times, PACI precipitates are composed of Al~ sub-
units with some polymerization of the octahedra
(Bottero et al., 1987; Bertsch, 1987). The shape and
size of the particles were dependent on ligand number
and age. For ~ -- 2.6, Bottero et al. (1987) observed
particles in chain-like clusters (diameter~0.1/zm);
at ~ = 3.0 and short aging times, particles consisted
14 -
PACL
12
10 ALum
E
6
4
I I I I I I f I I
0 20 40 60 eo 100 120 140 160 180
T i m e { rain )
Fig. 3. Reactivity of redissolved precipitatesof alum and
PACI with ferron.

WR 24~12--<3
1522 JOH~ E. VANBENSCHOTENand JA.~.SK. EDZWALD

of a mosaic of platelets (length ~ 0.04~/~m),
smaller size of these particles compared to the PACI
precipitates observed in this study is understandable
considering that the study methods reported here
involved pH adjustment (pH range from 5 to 10) and
flocculation to promote particle aggregation.
Solubility studies of alum and PACI were con-
ducted to gain insights to the dissolved Al speciation
and solid phases formed by precipitation of these
coagulants. Solubility diagrams are widely used as
an aid in interpreting coagulation results, although
the particular choice of dissolved species and solid
phase solubility product is somewhat arbitrary. The
AI(OH)3 solid phase has sometimes been assumed to
be amorphous (Edwards and Amirtharajah, 1985;
Dempsey et al., 1984), while another investigation
revealed a more crystalline solid phase (Dempsey,
1989). The existence of polymeric species is often
uncertain and in some cases polymers are assumed
to be present and in others only monomers are
considered. A review of AI hydrolysis studies reveals
a seemingly bewildering array of species and con-
stants to choose from, but as noted in a recent review
(Bertsch, 1989) many arguments for monomeric or
polymeric hydrolysis schemes are irrelevent since
many experimental results are system specific. The
specific conditions for AI hydrolysis following alum
addition in water treatment systems include the
following: relatively dilute AI concentrations, fast
addition of base if pH is adjusted during coagulation,
presence of sulfate, OH/Ai ratios > 2 and reactions
involving freshly precipitated solids. The first three
conditions are those for which monomeric forms of
Al are expected, although some uncertainty exists due
to the high ligand numbers that are characteristic of
water treatment conditions. It would be expected that
fresh precipitates formed in water treatment would
be a metastable, amorphous AI(OH)3(s). Freshly
precipitated AI hydroxide has often been character-
ized as amorphous (De Hek et al., 1978; Smith and
Hem, 1972; Hem, 1972; Hem and Roberson, 1967).
Although there is considerable evidence suggesting
that in the acidic pH range Al solubility may be
controlled by an Al-SO4 precipitate (Hayden and
Rubin, 1974; Singh, 1969), other investigators (De
Hek et al., 1978) dispute such findings.
The solubility of Al for alum and PACi additions
to deionized water at 20-25°C is shown in Fig. 4. For
alum, two Al doses were used as indicated by arrows
in Fig. 4. The soluble species used in constructing the
curve in Fig. 4(a) were Ai 3+, AI(OH)2+ and AI(OH);.
The dotted line is the theoretical solubility of Al if a
fourth monomer, AI(OH)~, is also included in the
calculations. Amorphous AI(OH)3 is assumed to be
the solid phase controlling solubility. AI hydrolysis
constants are shown in Table 2. A temperature of
25:C has been used in the calculations.
Although investigations of AI speciation in
water treatment have often included the AI(OH)~
monomer, the data shown in Fig. 4(a) clearly do
not correspond to solubility as defined by all four
monomers (another AI monomer, Al(OH) °, has been
postulated, although equilibrium constants are con-
sidered unreliable and the existence of the species is
often questioned). Whereas the hydrolysis constants
for AI(OH)2+ and AI(OH)~" are well established, the
constant for AI(OH)~" is considered to be too high
(Baes and Mesmer, 1976). Also, K,o values for
Al(OH)3(s) vary widely and depend on the type of
solid material present. Hayden and Rubin (1974)
report K~o= l0 -3L6 for amorphous AI(OH)3 which is
in good agreement with the AI solubility observed in
these studies for alkaline conditions. On the acidic
portion of the solubility diagram in Fig. 4(a), the
experimental data appear slightly more insoluble
than the theoretical curve. The data points near pH 4
are undersaturated with respect to the solid phase,
but the remaining points between pH 4.5 and 6.5

-2 -2 --

-3
,i • ".
/
( * "

-4
\ °
o E
l= -S

-S o
c:n
o
.J
-7 ALum

(o) (b)
-8 I I I I I I I -8
,
4 5 6 7 8 9 10 3 4 S 6 7 8 9 ~0
pH pH
Fig. 4. Experimental solubility data for dissolved aluminum in solutions of (a) alum and (b) PAC1 at
20-25:C. (a) Alum added at log Al z -3.3 (Q) and log Al ==- 4 (O) as shown by arrows. Solid line is
theoretical solubility of aluminum in equilibrium with Al(OH)3(am)(pK, = 31.5). Species include AP +,
Al(OH)z+ and AI(OH)~'. Dotted line is aluminum solubility if AI(OH)~"is included. (b) PACI added at
log AI = -3.3. Solid lines are theoretical solubility for specified A! species. Dashed line shows trend of
experimental data at slope of -7, the same as for the Al, polymer.
 Aluminum hydrolysis reactions
Table 2. Aluminum hydrolys/sconstants
Reaction
AIj÷ + H20 = AI(OH)2÷ + H ÷
AI~÷ + 2H20 = AI(OH)~" + 2H ÷
AI3+ + 4HzO = AI(OH)~" + 4H +
AI(OH)3(s) = AI~÷ + 3 O H -
indicate a more insoluble solid phase than theoretical
predictions.
Differences in test data at acidic and alkaline pH
were examined by calculating and plotting log AI3+
vs pH. The concentration of AP + was calculated
using the chemical equilibrium model MINEQL,
assuming that the three monomeric species discussed
previously were present. Theoretically, the slope of an
Al 3+ vs pH plot should be - 3 with an intercept equal
to log (K~/K~). Dempsey (1989) has shown that
between pH 4.75 and 6.5 a log Al 3+ vs pH plot
exhibited a slope of -2.96 and a K,o of 32.8 corre-
sponding to microcrystalline gibbsite. Assumed AI
species included Al 3+, AI(OH)2+, AI(OHH)~',AI(OH)°
and AI(OH)~-. In this study, a regression line for pH
> 6 yielded a slope of -2.99 and an intercept corre-
sponding to a log F~ = -31.5. Regression results in
the pH 5-6 range gave a slope = -2.4 and a log
K~o= -35.2. While the results above pH 6 suggest
that the precipitated material is amorphous AI(OH)3,
the lack of a slope = - 3 for pH < 6 is indicative of
either an incorrect choice of AI species or equilibrium
constants, or that soluble AI species are controlled by
a solid phase other than Al(OH)3(am). Interest-
ingly, theoretical solubility calculations for amor-
phous forms of both AI(OH)s and basaluminite
[AI4(OH)IoSO4.5H20, log K=24.0] (Lindsay and
Walthall, 1989) show that in the acidic pH
range, AI solubility is controlled by basaluminite.
Assuming SO~- is constant, a log AP + vs pH plot
for basaluminite solubility would exhibit a slope of
-2.5, which is close to the value observed in these
studies. However, because of a lack of direct exper-
imental evidence, the existence of a mixed AI-SO4
precipitate is uncertain.
The solubility data for PACI [Fig. 4(b)] show that
at a dose of 10-s3 M (13.5mg AI/I) the AI species
in this coagulant did not precipitate below pH 7. The
data in Fig. 4(b) include not only the solubility data
described previously, but also data points from exper-
iments with slow mixing periods of 4, 6 and 24 h.
These longer term tests, undertaken to determine if
kinetic factors were important in the precipitation
reactions, revealed no differences in precipitation
over time. Although PACI precipitates are known to
undergo structural rearrangement over time scales
as short as 24 h (Bottero et aL, 1987), such changes,
if they occurred, did not appear to significantly alter
solubility relationships.
Also included in Fig. 4(b) are theoretical lines for
All304(OHl)~ [pK = 98.73, Baes and Mesmer (1976)]
and AI(OH)~- in equilibrium and Al(OH)3(am).
Although the experimental data tend to follow
1523
pK Reference
pKI, " 4 . 9 9 Ball et aL (1980)
pK,2 = I0.I Ball e t a / . (1980)
PK,4 = 23.0 Ball et al. (1950)
pK., .. 31.6 Hayden and Rubin (1974)
the slopes of these lines, they are shifted toward
higher pH. The slopes are significant because on a
log Al vs pH plot, the slope of a line for a given
species is equal in magnitude to the the charge of
that species (note that the sign is reversed, how-
ever). The dashed line in Fig. 4(b) has a slope of
- 7 , the same as the line for the AI,3 polymer. The
data tend to follow this line, possibly indicating
that a highly charged polymeric species, or com-
bination of species, is controlling solubility in this
pH range. The data at alkaline pH are less soluble
than the theoretical curve for AI(OH)~'. This is
interpreted to mean that the solid phase in these
experiments is probably not an amorphous A1
hydroxide precipitate, an observation supported by
results of the timed spectrophotometric procedure
(Fig. 3).
Temperature effects
In Fig. 5, solubility data at 4°C (open circles)
are included in the solubility diagrams. For alum,
the dashed line is the theoretical solubility of Al
at 4°C. Compared to the data at 20-25°C,
there has clearly been a shift in solubility. The
standard enthalpy of AI(OH)3(s) is reported as
22.8kcal/mol (Smith and Martell, 1974) which
results in decreased Al solubility with temperature.
As discussed subsequently, decreasing temperatures
also result in changes in the ion product of water
and cause a shift in the solubility curve toward
higher pH.
The data at 4°C for PACI show a similar trend
above pH 7. The lines in Fig. 5(b) have been drawn
through the points to show data trends; they do not
represent theoretical solubility curves.
The results of tests using alum [10-3"3M
(13.5mgAl/l)] in deionized water are shown in
Fig. 6. At 25°C, stable particles were initially formed
at about pH 4.5 as shown by the peak in turbidity
and the decrease in the concentration of dissolved
aluminum. As the pH was increased, the precipitate
was destabilized as indicated by decreases in both
turbidity and EPM values. The isoelectric point
(pHli~) of the A! precipitate occurs at about pH 7.
Below pH 4.5 and above pH 8, most of the A! was
present as soluble species.
The effect of low temperature is two-fold. First,
the p H of precipitationwas increased to about 5.5.
Both turbidity and AI data illustratethis shift in
solubility.The second effectis that at 4°C, particles
appeared to maintain a positivecharge at higher p H
than at 20--25°C. The pI-l~ is increased to about
p H 9 at 4:C.
1524 JOHN E. V^N BENSCHOT-r~ and JAM~ K. EDZWALD

-2 -2
\
\\
-3 -:3
\ 25" ~e • o**** ~q~ e~*

-4 \ ,/0 o
E -5 -5
"~' o ;/
0
O~ - 6
..J
#
#~ -
/ /00% ~, - 6
o
-/ b/
-7 AI.um -7 -- PACL
(a) (b)
-8 I I I I I i -8 I I I I I I
4 5 6 7 8 g 10 4 5 6 ? 8 g 10
pH pH
Fig. 5. Solubility plots of dissolved aluminum for alum and PACI in deionized water at 25 and 4°C vs
experimental data. (a) Solid and dashed fines are theoretical solubility of aluminum in equilibrium with
Al(OH)~(am) (pK. = 31.5). Co) Solid and dashed lines drawn to show data trends and do not represent
theoretical solubility curves.

Results using PACI [5.04 x 10-' M (13.6 mgAl/l)] the same for each coagulant, the maximum turbidity
are shown in Fig. 7. Differcnccs between PAC! and for PAC! was about 1.4 NTU compared to nearly
alum arc evident. PACI does not appear to prccipitate 8 NTU for alum. A trcnd of higher turbidity with
until about pH 7 as shown by the dissolved AI data, alum has also bccn observed in tests involving coagu-
although turbidity and EPM data indicate particle lation of humic materials (see Part II, Van Bcnscho-
formation. Also, turbidity curves for PACI arc ten and Edzwaid, 1990). These differcnccs support the
shaped differently than those for alum. PACI exhibits conclusion that different solid phases have formed.
a gradual incrcase in turbidity, reaching a maximum EPM data show higher positively charged particles
value at about one pH unit above the pH of prccipi- for PACI than for alum, and the particles formed
ration. These data suggest that below pH 7 PAC! from PACi maintained a positive charge to pH 9
precipitated, but the resulting solid phase was not while those for alum did not. The availability of
filterable using 0.22 pm porc size membrane filters. positively charged particles over a wide range is an
For alum, the maximum in turbidity and the re- important consideration for coagulation of negatively
duction in dissolved AI occurred at almost the same charged colloids. The effect of temperature on PACI
pH. Furthermore, although the AI dose was nearly was less pronounced than for alum. Particle mobility

i • T"4~ PACL
1.0 0 T=2~C

o0 .:?: \
~ o -
3
I
4 5 6 7 8 9 10
I
'oo , I vr. :r
3 4 5 6 7 8 9 10
pH
pH

~, 1 -o- -.., CP

~[ - I "-o, e~
(i. ""
tu- 2 I l l I I I 0 I I I I I I n I
3 4 5 6 ? 8 9 1o 3 4 5 6 7 e 9 10
pH pH

f
12

,. E
9
6
3
I 0 I I
3 4 5 G 7 8 9 10 11 3 4 5 8 7 8 9 10
pH pH
Fig. 6. Experimental results for alum (5 x 10 -4 M Ai) in Fig. 7. Experimental results for PACI (5.04 × 10 -4 M AI) in
deionizcd water at two temperatures. deionized water at two temperatures.

data for PACI appeared to be affected by temperature
change to some degree, but effects of temperature
on turbidity and dissolved AI concentrations were
slight.
Tests involving alum and PACI in deionized water
reflect AI hydrolytic reactions since OH- was the
only complexing ligand that systematically varied in
the experiments. To examine the effect of ligand
concentration on jar test results, the data for alum in
Fig. 6 were replotted as Fig. 8 with pOH as the
independent variable rather than pH. The results
show that the effect of temperature appears to be
largely accounted for by changes in the OH- concen-
tration. The standard enthalapy of reaction for the
dissociation of water is 13.36kcal (Garreis and
Christ, 1965) resulting in a change in the ion product
of water, K~, from 10-I( at 25°C to 10-j4s at 4°C.
Consequently, at constant pH, the hydroxyl ion
concentration decreases with decreasing temperature.
In addition to the ion product of water, temperature
would also affect the solubility product of AI(OH)3(s)
as well as intrinsic surface ionization constants.
Although possible effects on these constants is recog-
nized, from a practical standpoint the effect of OH-
is of most interest since pH can be controlled.
These results illustrate that aspects of particle
formation are temperature dependent. It has often
been reported that treatment plant performance is
adversely impacted by cold temperatures. For alum,
the effects of cold temperatures should be diminished
by an increase in pH. At 4°C, for example, an increase
of approx. 0.8 pH units (e.g. practicing coagulation at
I-- ALUM
z
D
.O
k.
I /
I- 0~,¢- I. _"~_J-,a Ae.L ~
-'~
lo 9 8 7 6
pOH
-, I- °\
LU 10 9 8 7 6
pOH
o I
11 t0 9 e 7 6
pOH
Fig. 8. Experimental data for alum (5 x 10-4 M AI) in
deionizedwater at two temperatures. Abscissa valuescalcu.
lated as pOH = p/~ - pH, where p/~ is 14.0and 14.8at 25
and 4°C, respectively.
Aluminum hydrolysisre~'tions 1525
pH 6.8 rather than pH 6) should result in similar
trends in AI solubility and particle stability as occur
for alum coagulation at 25°C at pH 6 (Figs 5 and 6).
Relationships between temperature, pH and treat-
ment performance have been observed by Camp et al.
(1940) in a study involving ferric salts. It was found
that adverse effects of cold temperatures could be
mitigated by an increase in the coagulation pH of
about 0.5 units. Similar findings were reported by
Mohtadi and Rao (1973).
For PACI, the results of replotting data with pOH
as the independent variable showed a divergence in
the curves. In contrast to alum which hydrolyzes/n
situ, the Al species in PAC! are preformed and the
precipitation of PACI results in a different solid phase
than the amorphous AI(OH)3 precipitate formed
from alum.
CONCLUSIONS
Based on the results of this research, the following
conclusions are made.
(l) The hydrolysis o r a l following addition of alum
to deionized water at concentrations typically used in
water treatment shows little evidence of polymer
formation. Al solubility can be adequately described
by the presence of three monomeric species: AP +,
Al(OH)z+ and AI(OH)~'. Application of a timed
spectrophotometric method to alum in deionized
water showed that Al was present as monomers
almost entirely.
(2) PACI was characterized by a timed spectro-
photometric method which showed that approx. 90%
of the A1 was in a polymerized form. When used in
e Tm,~C
jar test type studies at pH < 6, the Al polymers were
0 T = 2~BC
stable in dilute solutions and for the time scales
typical in water treatment.
(3) Experimental results including analysis of redis-
~. I I solved precipitates, solubility tests, turbidity data and
S 4 3 EPM measurements indicated that alum and PACI
precipitate to form different solid phases. The poly-
meric structure remains intact within the PAC! pre-
cipitate and particles are more positively charged and
produce lower turbidity than alum floe.
(4) Temperature exerts a strong effect on solutions
containing alum. Turbidity, electrophoretie mobility
and Al solubility are temperature dependent. The
5 4 3
underlying effect has been shown to be chemical in
nature. Al hydrolysis can be viewed as a complex-
ation reaction involving hydroxyl ions. At constant
pH, the hydroxyl ion concentration changes with
temperature due to the temperature dependence of
the ion product of water. The data suggest that when
using alum, some of the adverse effects due to cold
I
5 4 3 temperatures may be offset by an increase in the
coagulation pH.
(5) PACI is much less affected by temperature than
alum. At constant pH, low temperature produces
only minor changes in turbidity, electrophoretic
mobility and Al solubility. Although the precipitation
1526 JOXN E. V^~ B~SSCMOT~and JAMESK. EDZWALD
mechanisms for PACI appear to be different than for
alum, the fundamental mechanisms are not clearly
understood.
Acknowledgements--The research described in this paper
has been funded, in part, by the Risk Reduction Engineering
Laboratory, U.S. Environmental Protection Agency (U.S.
EPA), under Cooperative Agreement CR-812639. The
assistance of Kim R. Fox, U.S. EPA Project Officer, is
greatly appreciated. The content and conclusions are the
views of the authors and do not necessarily reflect the views
and policies of the U.S. EPA. Mention of trade names or
commercial names does not constitute endorsement or
recommendation for use.
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