JOUI~N~kL OF COLLOID AND INTERFACE SCIENCE" 24, 47-55 (1967)

Coagulation and Reversal of Charge of Lyophobic Colloids by

Hydrolyzed Metal Ions
IV. Chromium(Ill) Nitrate and Perchlorate1' z
S T A N K A K R A T O H V I L AND E G O N M A T I J E V I C

Department of Chemistry and Institute of Colloid and Surface Science, Clarkson College of Technology,
Potsdam, New York 13676
Received January 7, 1967

The coagulation and the reversal of charge of silver bromide sols by freshly pre-
pared and aged solutions of chromium(III) nitrate and ehromium(III) perchlorate
has been investigated. The aging was accomplished either by storing the chromium
salt solutions at room temperature or by heating these at 90°C. for various periods of
time. The "log. concentration chromium salt vs. pit" domains of coagulation and of
stabilization due to the reversal of charge have been determined. The results are dis-
cussed in light of the existing information on the hydrolysis and polymerization of
chromium(III) ion.

INTRODUCTION various hydrolyzed complexes of chromium

I t has been shown in the previous com-
munications of this series that the coagula-
tion and reversal of charge phenomena of
lyophobic hydrosols b y polyvalent metal
ions are greatly influenced b y the hydrolysis
products of these ions. Since various metal
ions are subject to different eomplexing in
aqueous solutions and the hydrolysis species
are usually not known with certainty, it i s - -
as a rule--impossible to predict the coagula-
tion and reversal of charge effects caused b y
the salts of these ions. Instead, systematic
investigations must be carried out in order
to determine the interaction of these ions
with lyophobie colloids as a function of salt
concentration, pit, age, etc.
The hydrolysis of c h r o m i u m ( I I I ) ion has
been a subject of m a n y investigations owing
primarily to the interests of leather chemists
in the tanning properties of chromium salt
solutions.
There is ample experimental evidence t h a t
1 Supported by the U. S. Army Research Office
(Durham), Grant No. DA-ARO (D)-31-124-G656.
Part III, see reference 1.
47
ion are formed when chromium salt solutions
are (a) prepared b y dissolution of salts in
water, (b) reacted with base, (c) aged at
room temperature, and (d) heated for various
periods of time in absence and presence of
base. Complexes involving anions other t h a n
O H - will not be included in the discussion
t h a t follows. I t has been established t h a t
nitrate and perehlorate ions show no ten-
dency to form " p e n e t r a t e d " chromium
species (2-4). Only c h r o m i u m ( I I I ) - n i t r a t e
and -perchlorate have been used in this
work.
Despite intensive efforts by m a n y investi-
gators little definitive evidence is available
on the nature and the composition of hy-
drolyzed chromium species. Indeed, there is
a great deal of conflicting information with
regard to the hydrolysis process of chro-
m i u m ( I I I ) ion. E v e n the intensive change in
color from purple to green in the course of
the hydrolysis process does not seem to be of
much use in the evaluation of the hydrolyzed
species. I f one disregards a great m a n y specu-
lative conclusions which are common in
48 KRATOI-IVIL AND MATIJEVIC

aqueous chemistry of chromium ion (5-7) many studies (2, 5, 10, 20-25). Sufficient
the following facts seem to be reasonably well evidence is available to indicate that reflux-
established .3 ing of chromium salt solutions in absence of
Chromium(III) salts hydrolyze immedi- base yields only dimers (2, 14, 16, 17, 24-26)
ately upon dissolution in water to form Cr2(OH)~ + or Cr2OH 5+ and trimers (2, 25)
CrOH ++ species (8-10). The values for the Cra(OH)~ + or Cra(OH)~ +. No hydrolysis con-
hydrolysis constant at 25°C. have been given stants are given for any of these species.
as K1 = 1.1 X 10-4 (11), 1.58 X 10-4 (12), Reports as to the time of heating required to
and 9.8 × 10-5 (8, 9). reach "equilibrium" vary considerably (2,
The hydrolysis is promoted considerably 10, 19, 20, 24, 25). It appears that after
by the addition of base. No precipitate is several days of refluxing the aging process
formed if the addition of strong base is less becomes so slow that a quasi-equilibrium
than one mole per mole of chromium salt may be assumed. There are also conflicting
(33.3 % basic). When more base is added reports as to the fraction of the chromium
chromium hydroxide will precipitate but salt that is hydrolyzed upon refluxing.
will eventually redissolve (13, 14). Clear Whereas in some eases complete hydrolysis is
chromium salt solutions were obtained even assumed (2, 10), in others less than 30%
with base content of over 2 moles per mole (20, 24) is believed to be in hydrolyzed form
of chromium (5, 14, 15). in solutions of approximately the same con-
There is some disagreement in the litera- centrations of chromic salts.
ture as to the nature of the hydrolyzed Solutions to which base is added before
species in ehromium(III) salt solution which heating appear to be still further hydrolyzed.
are <33.3% basic. According to Bjerrum Most of the authors assume the formation of
(9) the species are the same as in pure aque- more highly polymerized olated or even
ous solutions (CrOH ++) but in larger quanti- oxolated chromium polymers. No attempt
ties. Also a small amount of Cr(OH)2 + was was made to identify these species, which
detected. The latter, for example, never ex- apparently are polydisperse and therefore
ceeds 5.5 % in a 0.01 molar solution of CrCls. difficult to formulate.
Others have suggested olated polymerized It seems that no study of coagulation and
species, most frequently in dimeric form reversal of charge properties of chromic solu-
[Cr2(OIt)~ +, Cr204+] (10, 14-17). However, tions has been made so far. It was observed
the olation may be due to the aging of the that chromium salts interfere with coagula-
solutions because the measurements were tion of silver chloride in analytical chemistry,
done following various times of "equilibra- giving peptized, nonfilterable sols (zi). It was
tion." It has been known that chromium salt also found that complex chromium ions tend
solutions change on standing, and apparently to adsorb on various adsorbents (27).
Stiasny was first to suggest that olation In this paper a systematic study of
processes were responsible for these changes coagulation and reversal of charge phenom-
(5, 10). There is a great deal of conflicting ena of silver bromide sols by aqueous chro-
evidence as to the period of time necessary mium(III)-nitrate and -perehlorate solutions
for a solution to "equilibrate" by aging at is reported. The effects of pH, the age, and
room temperature (4, 10, 18, 19). It is most the mode of preparation of the solutions are
likely that aging is a slow and continuous investigated and the results interpreted in
process, resulting finally in precipitation of light of the hydrolysis processes. Complete
chromium hydroxide. No conclusive in- "cone. chromic salt-pH" domains are given
formation is available on the composition of for fresh and aged solutions of Cr(III)-salts.
the intermediate complex hydrolyzed spe- EXPERIMENTAL
cies.
Forced aging by heating the solutions of Materials. Chromium(III) nitrate (Fisher
ehromium(III) salts has been the subject of Certified Reagent) and chromium(III) per-
chlorate (K & K Rare and Fine Chemicals)
Water of hydration will be disregarded in the were used without further purification. All
discussion to follow. other chemicals were of the highest purity
 COAGULATION AND REVERSAL OF CHARGE OF LYOPHOBIC COLLOIDS
grade. Only doubly distilled water from an
all-Pyrex still was used for the preparation of
solutions. The concentration of chromium
salts stock solutions was determined by
gravimetric analysis.
Silver bromide sols in statu nascendi were
prepared by mixing solutions of silver nitrate
and potassium bromide to give a sol con-
taining 1 X 10-~ moles/liter AgBr and an
excess of 4 X 10-4 moles/liter KBr.
Aged silver bromide sols were prepared as
described earlier (28).
Preparation of Solutions. One-tenth molar
stock solutions of ehromium(III) nitrate or
ehromium(III) perehlorate were prepared by
weighing out the appropriate amounts of
solids and then analyzed for the concentra-
tion of ehromium. All dilutions were
obtained from these stock solutions using
doubly distilled water. For experiments car-
ried out at 3°C., the stock solutions were
prepared and kept at this temperature at all
times.
No change in behavior of solutions aged
up to 10 days could be observed and there-
fore these solutions are referred to as fresh in
the subsequent discussions.
For the study of aging effects, solutions of
various concentrations were kept at room
temperature for periods of time up to one
year. These solutions will be called "time
aged."
Forced aging at elevated temperatures was
accomplished b y keeping 2 X 10-4 M solu-
tions of chromium(III) salts in glass-stop-
pered Pyrex flasks at 90°C. for various
periods of time. Afterwards the solutions
were cooled quickly to room temperature and
all experiments carried out at 25°C.
Methods. Coagulation. The procedure for
the determination of the eritieal coagulation
concentration (e.e.e.) and the critical stabili-
zation concentration (e.s.e.) has previously
been described in detail (29, 30). The sys-
tems were prepared by mixing the contents
of a pair of test tubes from two series. One
series of test tubes contained equal volumes
of silver nitrate at constant concentration
and chromium(III) nitrate (or perchlorate)
in gradually varying concentrations. The
other series eontained equal volumes of the
potgssium bromide solution at constant con-
49
centration to which nitric acid or sodium
hydroxide were added as necessary to adjust
to a desired constant pit. In part of the
experiments the concentration of chromium
salt was kept constant and the concentration
of acid or base was varied to systematically
change pit. The final volume of all systems
after mixing was 10 ml., and all concentra-
tions are expressed in terms of this volume.
Turbidity changes were measured with an
Aminco light-scattering photometer using
the 546 m~ mercury line. The data are re-
ported as "scattering intensities" and are for
10 min. reading. These "scattering inten-
sities" are equal to turbidities when particles
are small and the sols dilute.
Electrophoresis. Mobilities of the colloidal
particles were determined using the _-VIattson
type cell as described earlier (28). These
measurements were carried out with aged
silver bromide sols and with sols in statu
nascendi in presence of different eoncentra-
tions of fresh and aged solutions of chromium
nitrate and at different pH. Mobility
measurements were made at room tempera-
ture 10 rain. after mixing of solutions.
Measurements of pH. A Beckman Model
GS ptI meter with glass electrodes was used
and calibrated regularly with appropriate
buffer solutions before and after each set of
measurements.
RESULTS AND DISCUSSION
Figure 1 gives a number of coagulation
curves for a negative silver bromide sol in
statu nascendi obtained with the same solu-
tion of chromium(III) nitrate aged at room
temperature for various periods of time. The
critical coagulation concentration (c.c.e.),
determined by the extrapolation of the steep
part of the coagulation curve to zero turbid-
ity, remains the same for solutions aged for
up to 10 days. An identical c.c.c, is also
found with solutions prepared and stored at
3°C. Since at this low temperature the aging
process is extremely slow, one can assume
that no significant changes have taken place
in chromium salt solutions kept for less than
10 days at room temperature. Older solutions
show a significant shift towards a lower e.c.c.
The slow rate of chromium(III) ion hy-
drolysis at room temperature was observed
before (14, 16, 19), and our coagulation data
50 KRATOHVIL AND MATIJEVIC

p.o~.NO.._0 i
A(jBr/Br-
o.~ o-~o-., r~ \~~-.. /
~ / ~ ~ /! \~ /

°
~Z 0"16
'o.-,
pH at C.C.C. \ I I . : ; i

t ; 41; \1~ i : ~ "1 ..o.

o
<°'°e --- 4:5--~,/I . I : : .'"
m . . . . 5.o ~/I; I ~~ / /"
. .

.... ~ i\1, I ~ • • .': "

:-..: i ! I ,, t.. i
-3.5 -4.0 -4.5 -5.0 -5.5
LOG. MOLAR CONC. OF Cr(N03) ~.
F r o . 1. C o a g u l a t i o n c u r v e s of a silver b r o m i d e sol i n statu n a s c e n d i in t h e p r e s e n c e of v a r i o u s a m o u n t s
of c h r o m i u m n i t r a t e , 10 m i n u t e s a f t e r m i x i n g t h e r e a c t i n g c o m p o n e n t s . T h e age of t h e c h r o m i u m n i t r a t e
solution: -- f r e s h ; . . . . 8 d a y s old; . . . . . 2 m o n t h s old; . . . . . . 4 m o n t h s old; . . . . . . o v e r 6 m o n t h s old;
. . . . . . I y e a r old. S q u a r e s 3°C., circles 25°C. ; p t I at c.c.c, as i n d i c a t e d on t h e d i a g r a m . A g B r : 1 X 10-4 M,
p B r - : 3.4.

are in agreement with these findings. Co-
agulation results also indicate that the aging
process continues for periods of over one
year. The solutions aged for one year gave a
coagulation curve distinctly different from
the rest of the curves. I t is impossible to say
if this is entirely due to the hydrolysis of
chromium ion or whether some other proc-
esses have taken place (dissolution of glass,
etc.).
I t is also to be expected that the change in
p H will influence the e.e.e. Experiments were
carried out at various p H values using chro-
mium salt solutions of different ages. A sum-
mary of the results is given in Fig. 2, which
shows the "log ehromium(III)-salt-pH" do-
main for fresh and time-aged chromium salt
solutions. Circles give the e.c.e, data as ob-
tained with fresh ehromium(III) nitrate so-
lution and are reproduced from our
preliminary report (31). Added are results
obtained at 3°C. with ehromium(III) nitrate
(blackened circles) and at 25°C. with fresh
solutions of chromium(III) perehlorate (di-
amonds). All these systems were obtained
using a concentration gradient of chromium
salts and the results are quite similar.
Squares give the c.s.c, boundary and the
points were determined using a p H gradient.
The boundary of the coagulation range of
chromium(III) nitrate solutions aged at
room temperature for 6 months is delineated
by triangles. For a given ptI the e.c.c, of
aged solutions is ahvays lower than that of
fresh solutions.
The coagulation concentration of fresh
solutions at low p H values ( < 3) is N 2.6 X
10-5 M, which is characteristic for trivalent
counterions (32). No reversal of charge is
observed even at the highest additions of
salt. This confirms the existence of CP + ion
as the predominant species. As the p H in-
creases ( > 3 ) the e.e.e, also increases indi-
cating the presence of lower charged species.
As was mentioned before CrOH ++ (and
negligibly small amounts of Cr(OH)2 +) seem
to be the only hydrolysis products under the
experimental conditions employed. Using the
mean value for the reported first hydrolysis
constant (8, 9, 11, 12), we can calculate that
at the c.e.e, at a pH of 3 about 9 % and at a
plI of 5 about 90 % of total chromium should
exist in hydrolyzed form. If this were the
case the e.c.e, would have to be somewhat
 COAGULATION AND REVERSAL OF CHARGE OF LYOPHOBIC COLLOIDS 51

r ---- agulation properties which can be explained

AgBr~l.[O-4M I~
pBr, 5.4 N ~" assuming the formation of olated species as
-2% r3'~-- has been suggested before (10). Previous
...a evidence indicated that the main hydrolysis
o* product is a dimer, Cr2(OH)~ +. Coagulation
A results indicate that in addition to the dimer,
~-3.c
~, ~~[] species of higher charges must be present.
At the lowest p H the e.c.c, corresponds to
....% A/,, counterion of 4 + charge, but this appears to
O D\
z be coincidental. Firstly, this would imply
5 that all of the chromium has been
u_
o -4,C hydrolyzed, which is known to be false.
n~°°zC5 u//
Secondly, if solutions were completely hy-
drolyzed to Cr~(OH)~+, reversal of charge
EXTENDED COAGULATION REGION / I would take place at concentrations slightly
d<
0 higher than the c.e.e., which does not occur.
Finally, a plateau in the c.c.c.-pH curve
would be apparent if only one species were
present. Olated species of charges higher
than + 4 in time-aged solutions were sug-
-6.0 gested by others, but neither previous work
2.0 :5.0 4.0 pH. 5.0 6.0 nor coagulation data can be used for their
FIG. 2. The log Cr(NO3)3 or Cr(C104)3-ptt identification.
domain for a silver bromide sol in statu nascendi The increase in c.c.c, with increasing p H
using fresh and time-aged solutions of chromium can be explained if it is assumed that olated
salts. Symbols: diamonds, fresh solution of Cr species in aged solutions become oxolated
(C104)3 at 25°C.; blackened circles, fresh solution upon addition of base, which leads to lower
of Cr(NO3)3 at 3°C.; open circles, fresh solution charged species. Thus, the entire process
of Cr(NO~)3 at 25°C. (points obtained using a during time aging and subsequent alkaliniza-
gradient of Cr(NO3)3); squares, fresh solution of tion can be presented in a simplified manner
Cr(NO3)~ at 25°C. (points obtained using a gra-
as follows:
dient of pH); triangles, solution of Cr(NO3)8
aged for six months or more. Measurements taken dissolution
10 minutes after mixing of the reacting compo- in w a t e r

nents. 2Cr+++ ~ ' 2CrOH++

higher at pH > 4. Coagulation results would
indicate that about 70% of chromium is
hydrolyzed to Cr(OH) 2+.
When a sufficient amount of C r ( O H / + is
present in solution, the adsorption of these
ions causes charge reversal as given by
squares in Fig. 2. To confirm this, electro-
phoretic mobilities of an aged AgBr sol were
measured in presence of three different con-
centrations of fresh chromium(III) nitrate
solutions. The results are given in Fig. 3 as a
function of pH. As expected, with increasing
ptI the originally negatively charged sols
become strongly positive. The zero point of
charge is higher the lower the concentration
of added chromium salt.
Time-aged solutions show enhanced co-
aging NaOH
' Cr2(OH) ~+, * Cr20~ +
Obviously additional equilibria should be
written to account for the existence of other
hydrolyzed species.
The effect of forced aging by heating of
chromium(III) nitrate solutions at 90°C. for
various periods of time is presented in Fig. 4.
After only ~-~1 hour of aging at 90°C. the
solutions show approximately the same in-
crease in coagulation ability as solutions
aged for over 6 months at room temperature.
Solutions heated for longer periods of time
coagulate at still lower c.c.e. In addition,
these solutions very strongly reverse the
charge of the silver bromide sol particles as is
manifested in the sharp turbidity drop at
52 K R A T O H V I L AND M A T I J E V I C

Cr(NO~)~,: /
_ 2.0.10-4M

o~ / / / / / / / ~
~.-2- I
8.0. IO-SM
~-. 0 ~//////i/1~///////////////~
5--a-
m
I
:~° 2- [0
5.0.1 -sin'"
"/////////////////"//////~ I
/

2.0 3.0 4.0 5.0 6.0

pH.
FIO. 3. Mobilities of an aged silver bromide sol (AgBr 1.10 -4 M; p B r - : 3.4) in presence of three differ-
ent concentrations of fresh solutions of chromium (III) n i t r a t e as a function of pH. H a t c h i n g represents
the coagulation range.

AgBr: I.IO-4M
/ ~ _ _ o __ o - - o --, pBr: 3.4
0.24
U
>:
t--
Z
Ld
pH QI
-
------
.....
-
C.C.C.
4.5
5.5
5.8
I ::l
O'. I.

t - 0.16
Z 5.7 - - 1-
(.D
Z
-' 6.0
i B../L":.'i i
LIJ
I--
I-
<
?!i\
0.08 io. i \; i 5t

I<: i'i !
t
-4.0 -4.5 -5.0 -5.5 -6.0
LOG. M O L A R CONC. OF Cr(N03) 3.

FIO. 4. Coagulation curves of a silver bromide sol in statu nascendi in presence of chromium n i t r a t e
solutions aged by heating for various periods of time at 90°C. Points are obtained 10 minutes after mix-
ing the reacting components at 25°C. Time of aging of solutions: - - fresh solution; --- 50 rain.; . . . .
20 hr. ; . . . . . . 48 hr. ; . . . . 4 days. pH at C.C.C. as indicated on the diagram.

concentrations somewhat higher than the changes were observed if solutions were aged
c.c.c. B y extrapolation to zero turbidity of at 90°C. for more than 4 days.
the limit " B " one obtains the critical stabili- The change in p H exerts a considerable
zation concentration (c.s.c.). No significant effect upon the c.c.c, of the heated solutions.
 COAGULATION AND REVERSAL OF CHARGE OF LYOPttOBIC COLLOIDS 53

0.24 /.~ ,--o AgBr : I • I0- 4M

1 pBr: 5.4

LO OJC

- 14.9-6.2/ / )~ i4..s IS.2 \2.2

g ~ c.0.0.5.9, ;17: . '. i1 \
Io ! \
m 5.2 6.8.."" /
=c.c. 6.6<~"
..." :/.Io I ~ ": i. i I I

o o .... ~.4r
..y.Y/:Jt 6.---k)-----:,o-.-8.-.6--o~o
l ,
-5.0 -5.5 -6.0 -6.5 -7.0
LOG. MOLAR CONC. OF Cr(N03) 3.

Fro. 5. Effect of pH upon the coagulation curves of a silver bromide sol in statu nascendi using chro-
mium nitrate solutions aged 4 days at 90° C.

Figure 5 gives a number of coagulation

curves obtained with c h r o m i u m ( I I I ) nitrate
II AgBr/Br-
pH, 57-5.9
0.24
solutions aged for 4 days at 90°C. but at I %
9-- .--o~ I j
different p H values. This was accomplished .-to..
b y addition of various amounts of nitric acid
z
just before the solutions were used for co- "~ 0.16
_z
agulation. I n more acidic systems the c.c.c, is l :5
considerably lower. The effect of p H upon 7
c.s.c, is rather small.
For illustration, Fig. 6 gives three coagula- 0.06
tion curves obtained at the same p H at 25°C.
with the same c h r o m i u m ( I I I ) nitrate solu-
tion, which was (a) used fresh, (b) time aged
for 6 months, and (c) heated for 4 days at -4.0 -45 -5.0 -5.5 -6.0
90°C. I t is evident t h a t time-aged solutions LOG. M O L A R CONC. OF Cr(N%) 3

coagulate better t h a n fresh solutions but do
not restabilize the sol b y charge reversal.
Heated solutions coagulate at still lower con-
centrations and strongly reverse the charge.
Figure 7 represents the "log Cr(NOa)a-
p H " domain for c h r o m i u m ( I I I ) nitrate solu-
tions fresh and heated 4 days, respectively.
The difference between the two is quite
remarkable. The c.c.c, of heated solutions is
considerably lower ( ~ 2 or more orders of
magnitude) and the charge can be reversed
over the entire p I I range. All this indicates
t h a t heated solutions are extensively hy-
drolyzed and contain complex species of
higher charges. At p H <3.5 complex ions
FIG. 6. Coagulation curves of a silver bromide
sol in statu nascendi in the presence of chromium
nitrate solution: - - fresh; --- aged over six
month G at room temperature and .... aged 4
days at 90°C. AgBr: 1 X 10-4M; pBr-: 3.4; pI-I:
3.7-3.9. Readings taken 10 minutes after mixing
the reacting components at 25°C.
must be of charges higher than -+-4. In 60
hours refluxed solutions Hall and Eyring (2)
detected species of the composition Cr2OH s+
and Cra(Ott)~ +, whereas Finholt (25) sug-
gested the presence of Cra(OIt)~ +. Coagula-
tion data would then confirm the existence of
such highly charged ions in heated chromium
54 KRATOHVIL~AND MATIJEVI(~
-2.0
• -3.0
z0
~3
h
0 -4.0
(5
Z
0
o -04.~
n,"
J -5.0
¢5
o,
-6.0
3.0 4.0 5.0 6.0 ~O
pH.
FIG. 7• The log Cr(NO~)3-pH domain for a silver
bromide sol i n statu nascendi using fresh solutions
of chromium(III) nitrate (O), and solutions of
chromium(III) nitrate aged by heating at 90° C.
for 4 days ([:3) and 5 days (A).
salt solutions. Between p H ~ 3 . 5 and 5.5 a
pIateau in c.c.c, is observed, corresponding
to -t-4 counterions. Over this range
Cr2(OH)~ + appear to be the predominant
species. The abundance in hydrolyzed ions is
substantiated b y the reversal of charge•
A number of experiments were carried
out with the so-called "basic" chromium
nitrate solutions• These are solutions to
which sodium hydroxide was added in defi-
nite molar proportions• Stock solutions were
prepared containing 0.1 moles/1, chromium-
(IIl) nitrate and NaOH to give molar ratios
of CP+: OH- 1 : i, 1 :1.5,and 1 :2.All solutions
were clear and of intense green color. The so
prepared solutions were then diluted prior to
coagulation experiments. Figure 8 gives
three typical curves as obtained with 33.3 %,
50.0 %, and 66.6 % basic solutions. With in-
creasing basieity both the e.e.c, and the c.s.e.
became lower. I t is interesting to note t h a t a
fresh 66.6% basic solution gives an about
identical curve as the solution aged for 4
0,24
pH at C.C,'C. AgBr/Br-
- -
------
5.5
5.7
'~
?
......... 6.0
J
/
.... 7.6
i •[6
:/
"4
i
10.08
$U \\ "i:.
'.:' \\.,
-4.5 -5.0 -5.5 -6.0
LOG. MOLAR CONC. OF Cr(NO~)3.
FIG. 8. Coagulation curves of a silver bromide
sol in statu nascendi in the presence of "basic"
solutions of chromium (III) nitrate. Molar ratio
of salt to base: 1:1 - - 1:1.5 ...... , 1:2 ...... .
Coagulation curve obtained with chromium(III)
nitrate solution aged for 4 days at 90°C. without
added base is represented by . . . . . . . . Readings
taken 10 minutes after mixing the reacting com-
ponents at 25°C. pit at C.C.C. as indicated on the
diagram.
days at 90°C• without added N a 0 H . This
would indicate t h a t aging b y heating and
basic making of solutions leads to formation
of similar or even identical olated species.
No a t t e m p t s were made to age "basic"
solutions. Work by other investigators has
shown t h a t under such conditions rather in-
volved polymerization processes take place
(2, 10) which are not easily understood.
The present investigations have shown
t h a t coagulation and reversal of charge of
lyophobic sols b y chromium nitrate solutions
can be accounted for if hydrolysis is taken
into consideration. These experiments con-
firmed again t h a t only hydrolyzed species are
responsible for charge reversal. T h e y also
show t h a t the coagulation of a lyophobic
colloid is extremely sensitive to the change
in charge of counterions due to hydrolysis.
The consistency of the coagulation data with
the formulation of hydrolyzed species as
proposed by others for various conditions of
c h r o m i u m ( I I I ) solutions gives additional
credibility to the existence of these com-
plexes.
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