International Journal of Mineral Processing, 11 (1983) 139--153 139

Elsevier Science Publishers B.V., Amsterdam -- Printed in The Netherlands

ADSORPTION AND FLOTATION BEHAVIOR OF MANGANESE

DIOXIDE IN THE PRESENCE OF OCTYL HYDROXAMATE

R. NATARAJAN *and D.W. FUERSTENAU

Department of Materials Science and Mineral Engineering, University of California,
Berkeley, CA 94720 (U.S.A.).
(Received March 3, 1982; revised and accepted December 6, 1982)

ABSTRACT

Natarajan, R. and Fuerstenau, D.W., 1983. Adsorption and flotation behavior of manga-
nese dioxide in the presence of octyl hydroxamate. Int. J. Miner. Process., 11: 139--
153.
The adsorption of octyl hydroxamate on electrolytic manganese dioxide was investi-
gated through adsorption studies, electrophoretic mobility measurements, infrared spec-
troscopy and Hallimond tube flotation. The adsorption measurements at room tempera-
ture and flotation studies show that a peak in adsorption density and flotation response
occurs around pH 9. IR spectra indicate the presence of basic manganous hydroxamate
complex at the surface. The electrophoretic mobility studies suggest that hydroxamate
adsorbs specifically at the manganese dioxide/water interface. Adsorption measurements
at an elevated temperature show that adsorption density increases with increasing tem-
perature. It is postulated that the reactive species in adsorption could be the hydroxamic
acid species.

INTRODUCTION

The selective flotation of minerals using chelating agents as collectors ap-

pears to be promising. Because the primary requirement for a collecting rea-
gent in flotation is that it must have a high degree of selectivity for the min-
eral being floated, the selective character of chelate-forming organic com-
pounds for metal cations makes them very attractive as flotation collectors.
Gutzeit (1946) was the first to review the application of various organic che-
lating agents as collectors and depressants. However, DeWitt and Batchelder
(1939) carried out a variety of experiments on the utilization of chelating
agents as collectors for copper minerals. Marabini and Rinelli (1973) investi-
gated a variety of chelating agents as potential collectors for oxidized lead
and zinc minerals. Hydroxamates have been tested as collectors for the flota-
tion of iron (Fuerstenau et al., 1970; Raghavan and Fuerstenau, 1975), cop-
per (Palmer et al., 1975), manganese (Palmer et al., 1975), rare-earths (Pradip,
1981), and other oxides; and in China they have been utilized industrially in
*On leave from the Ore Dressing Section, Bhabha Atomic Research Centre, Hyderabad -
16 (India).

0301-7516/83/$03.00 © 1983 Elsevier Science'Publishers B.V.

140

an oxidized copper flotation plant (W. Hu, pets. commun., 1982). Previous
work by Palmer et al. (1975) included investigation of the flotation behavior
and infrared characteristics of a manganese ore with hydroxamate. Those re-
searchers suggested that hydroxamate may be adsorbing through chemical
interaction between h y d r o x a m a t e ions and hydroxylated manganese species.
In the present study, an effort is made to understand the adsorption mecha-
nism of octylhydroxamate on manganese dioxide through adsorption mea-
surements, electrokinetic behavior, infrared spectroscopy, and Hallimond
tube flotation experiments.

THEORY

Hydroxamic acids, which may be regarded as derivatives of both hydroxy-

amines and carboxylic acids, can be represented by the general formula
R-CO-NHOH, where R usually represents an alkyl chain containing 6 to 8
carbon atoms. Because of this molecular configuration, a distinctive feature
of hydroxamic acids is their ability to form coordination compounds. The
detailed chemistry of hydroxamates and their iron complexes has been re-
viewed by Raghavan and Fuerstenau (1975).
Liu et al. (1975) have reported values of the stability constants of some
divalent manganese-hydroxamate salts (Table I), namely those of aceto-,

TABLE I

Stability values of manganous hydroxamates (after Liu et al.,1975)

Hydroxamic acid pKa logk I logk 2 log~2

Aceto 9.35 4.00 2.90 6.90

Butyro 9.48 4.23 3.35 7.58
Sorbo 8.80 4.50 3.51 8.01

butyro-, and sorbo-hydroxamic acids. Denoting the salt as MLi, where M

represents the bivalent metal ion, L the h y d r o x a m a t e anion, and i the num-
ber of groups, the stability constants were written as:
(MLi)
MLi.1 + L -~ MLi; k i =
(ML/.~) (L)
(MLi)
M + i L # MLi; //i = =k, k2 . . . .
(M) (Li)
The stability constants for octyl h y d r o x a m a t e with bivalent manganese are
not available, but it is reasonable to presume that t h e y are of the same order
of magnitude as those given in Table I. Basic manganous hydroxamates are
formed when a 1 : 1 mixture of bivalent manganese salt and hydroxamic
acid are alkalized. A dirty brown precipitate of manganous h y d r o x a m a t e
soluble in excessive alkali results at pH 8.7 (Bhaduri, 1956).
 141

The solid studied in this investigation, manganese dioxide, has a complex

crystal chemistry. It occurs most commonly in three crystallographic forms,
namely, a,/3, and 7, the latter material being used here. Being the most ac-
tive depolarizing agent, 7-MnO2 is extensively utilized in the manufacture of
batteries. The natural mineral form of 7-MnO2 is nsutite and the synthetic
form is produced by electrolytic deposition. An important feature of the
gamma-variety manganese dioxide is its nonstoichiometric character, having
a shortage of manganese ions with respect to the total oxygen attached to
either Mn4÷ or in the acidic hydroxyl groups. The formula often given for
these dioxides is MnOx in which the coefficient x is slightly less than 2. The
typical formula for the gamma-variety of manganese dioxide is MnO~.93
(Brenet, 1962).

MATERIALS AND METHODS

The manganese dioxide used in all the experiments was an electrolytic

variety supplied by Union Carbide Corporation. Spectrochemical analysis of
the sample revealed no impurities. The material as-received was ground to
minus 400-mesh in an agate ball mill and then cleaned by washing repeated-
ly in triply distilled water until the conductivity of the wash water was less
than 10 -6 mho. Final preparation of this material to be used for adsorption
and electrophoresis experiments involved filtering and air drying the mate-
rial. The surface area of this prepared sample as determined by B.E.T. nitro-
gen adsorption methods was found to be 6.7 m2/g. pH adjustments were
made with KOH and HNO3, and KNO3 was used to maintain the constant
ionic strength since the anions NO~ and C10~ are least likely to complex
manganese (Bailar, 1956).
Potassium octyl hydroxamate was prepared and purified in the laboratory
by reacting hydroxylamine hydrochloride with methyl octanoate according
to the method detailed by Raghavan and Fuerstenau (1975). Purified sodium
dodecyl sulfonate from Ben Den Chemical Co. was used in some of the flo-
tation experiments.
Adsorption isotherms were determined by the abstraction from solution
method, with the solution concentration be'rag analyzed spectroscopically
by the well-known ferric hydroxamate method (Neilands, 1966). To 2.5 cm 3
of hydroxamate solution, 5 cm 3 of ferric perchlorate was added and the ab-
sorbance of the purple~olored complex was measured at a wavelength of
512.5 nm in a Cary 17D UV-VIS-IR spectrophotometer. Adsorption mea-
surements were conducted in 50 ml Nalgene plastic bottles. In all the experi-
ments 0.2% solids were used. Adsorption experiments at an elevated tem-
perature were conducted in a constant temperature bath.
Infrared spectra for octyl hydroxamate, manganese dioxide conditioned
with water and octyl hydroxamate, and manganous hydroxamate precipi-
tated at pH 8.7 were obtained using the KBr pellet technique with a Perkin
Elmer IR 160 spectrophotometer.
142

Electrophoretic mobility experiments were carried out at room tempera-

ture with a Zeta Meter, using suspensions containing 0.05% solids by weight.
Figure 1, which presents a plot of the electrophoretic mobility against pH
at three levels of ionic strength (controlled with KNO3), shows that the iso-
electric point or the point-of-zero charge (PZC) occurs at about pH 5.6. This
value is in agreement with those reported in the literature (Healy et al.,1966;
Fuerstenau and Rice, 1968).
Flotation experiments were conducted with a modified version of the
Hallimond tube (Fuerstenau et al., 1957), using a 100 X 150 mesh size frac-
tion of manganese dioxide at 1% solids. A flotation time of 2 minutes at a
nitrogen flowrate of 45 ml/minute was selected for these experiments. Con-
ditioning with potassium octyl hydroxamate or with sodium dodecyl sulfo-

I I I 1 I I 1 I

)' - Mn 0 2
+2-
:E [3 IO "4 _MKNO~
(.3
O ~ "3 M
.J IO -2 M__
0
>
n-
LU
Q. +1-
o
~J
(/I

t)
:E

o
-J

o
I,-
uJ
0
a.
0
cc
I--
(J
i.i
PZCl -~~:~_
/
I.I
I
I
I
I I I I ,I I I I I
4 5 6 7 8 9 I0 II
pH

Fig. 1. The electrophoretic mobility o f 7 - M n O 2 as a f u n c t i o n o f p H a t various additions

of potassium nitrate.
 143

nate was carried out for 24 hours in all cases. The flotation experiments
were conducted without ionic strength control, that is, in the absence of
KNOs.

EXPERIMENTAL RESULTS

To determine the conditioning time required for achieving equilibrium,

preliminary experiments were conducted at two different temperatures for
various conditioning times. From the results presented in Fig. 2, it can be
seen that a period of about 24 hours is required to reach equilibrium. Conse-
quently, a conditioning time of 24 hours was chosen for all adsorption,
electrophoretic mobility and flotation experiments. All reported pH's are
final pH values.
Isotherms for the room-temperature (22°C) adsorption of hydroxamate
on manganese dioxide from aqueous solution at various pH levels are pre-
sented in Fig. 3. This figure shows that the hydroxamate adsorption density
I I I I I

¢q

~
40°C
0
$2
=E
3C Z~ " 22"C -
i¢1

0
o

bJ
I-
'~ 2c
=E
x
0
n-
o
>..
-r ~/f 2=10 "3 M KNO.3
l- pH 9.0
Z
~ m INIT, HXm CONC. 5xlO'4M

o W I I I I I
0 I0 20 30
ADSORPTION T I M E , HOURS
Fig. 2. The kinetics of hydroxamate uptake by ~-MnO 2 at 22°C and 40°C.
144

~ ~ r I I i I I I 1 ~ T I I I I 1
20 7" - Mn 0 2 ,,,t

o
2,1o-3 M K N03 2"
22"c
.~ ,o

MONOLAYER. . . . . . .

g .
g

o
•"r O. -
I I I I ,till I I I I I I III
10-5 10-4 10-3
HYDROXAMATE EQUILIBRIUM CONCENTRATION, MOLE/LITER
Fig. 3. Equilibrium adsorption isotherms for the uptake of oetyl hydroxamate at various
pH values by ~-MnO 2 at 22°C in the presence of 2 × 10-3M potassium nitrate.

increases with increasing equilibrium concentration and first tends toward a

constant value corresponding to monolayer coverage. The monolayer capac-
ity was calculated to be 7 × 10 -1° mole/cm 2 (represented by the dashed line
in Fig. 3), assuming the polar head area of the hydroxamate anion to be
25 A 2. The experiments carried out at pH 7.8 and pH 9.0 exhibited an ab-
rupt increase in adsorption density beyond the calculated monolayer capac-
ity at higher concentrations. This sharp increase appears as if chemical reac-
tion starts to occur at the surface, precipitating manganous hydroxamate.
Replotting these data as a function of pH for several equilibrium concentra-
tions (Fig. 4) shows that a peak in adsorption density occurs around pH 9.
Since the adsorption studies at room temperature (22°C) seem to indicate
some sort of chemical interaction of hydroxamate with manganese dioxide,
the effect of temperature on the adsorption process was investigated. From
the results given in Fig. 2, it can be seen that the amount of hydroxamate
adsorbed increases with temperature although the time required to attain
equilibrium does not change. Accordingly, adsorption experiments were car-
lied out at 40 ° C at pH 9 using 24 hours for equilibration, and the results are
plotted in Fig. 5. Clearly, temperature has the greatest effect above mono-
layer coverage where chemical reaction may be occurring at the surface.
 145

I0
I I I I I I !
Mn0 2
2x10"3 _M K N 0 3 , ?.2"C
N
:E
5 "I0 "4 1
V 2 x l 0 .4 J M HXm
LU
- 8 r'l I Xl0 "4
o
:E
O
rr
¢.)

>_-
I--
6-
z
bJ
o
z
0 --

n-
O
o

td

X
0
n-
>-
-r
Z
0 I I l I 1 I I I
4 5 6 7 8 9 I0 II
pH
Fig. 4. The effect of pH on the adsorption of hydroxamate on 7-MnO= at 22°C and 2 ×
10 -SM potassium nitrate, using three different equilibrium concentrations of hydroxa-
mate.

The effect of potassium octyl hydroxamate (KXm) on the electrophoretic

mobility of manganese dioxide was measured as a function of pH, and the
results are plotted in Fig. 6. In the absence of hydroxamate, reversal in the
isoelectric point (IEP) occurs around pH 5.6, which is the PZC under these
conditions. Fuerstenau and Rice (1968), working with three different varie-
ties of natural manganese dioxide, reported PZC values at pH 4.2, 5.6 and
7.4. Healy et al. (1966) also reported the PZC of electrolytic manganese
dioxide to be pH 5.6. The results show a distinct shift in the IEP due to the
presence of hydroxamate, indicating specific adsorption of hydroxamate
anions or formation of a chemical compound at the surface. In order to
provide more information, manganous hydroxamate was precipitated from
aqueous solution (Bhaduri, 1956) and its electrophoretic mobility was also
146

i I I I I I I J 1 u I I I I I I I

N 40-
~E

o O
o Z(5-
Q: O

~ IOm
~ -
Z -

"~
£3 - MO NOL ER
7
2
~ -

£E Y - MnO 2
0
(.,'3
c3 2 x I0 - 3 M KNO 3
'~ pH9
w
" 0 4 0 °C
,~ Z~ 2 2 "C
0
n-

-1- lOJ5 10 - 4 IO "~

HYDROXAMATE EQUILIBRIUM CONCENTRATION, MOLE/LITER

+3-- I I I I I I I I
y -MnO 2
I--
._1
o 2,,10-3M K N 0 3 , 22°C
> +2--

~(~ r'l I =¢10"4M "j

.~.\ v z,,o",, ~ AOOEO
+l- N\\ " s,,o";l .x,.
"~'"~ o , , ¢ , . ~ • ,,. (x-h ,P,.

5 -2- "'-.O ~ . _ ~

Or -3-- " " " "D

J
"' -. I I I l I I 1
4 5 6 7 8 9 I0
pH
 147

measured as a function of pH. The results (Fig. 6) clearly show that

manganous hydroxamate is negativelycharted even at pH 4.6.
The infrared spectra of potassium octyl hydroxamate, manganese dioxide
conditioned with water and hydroxamate, and manganous hydroxamate pre-
cipitated at p H 8.7 are presented in Fig. 7. The spectra of manganous hy-
droxamate precipitate and manganous dioxide conditioned with hydroxa-
mate are similarto those reported by Fuerstenau et al. (1970).
I I 1 I I
Mn02 .~.
'00h CONDITIONED WITH W A T E R . ~ ~
t

60 K CT L
40-- ~ HYDROXAMATE.,~j / I"

,,, 0 I
0 I I I I 1
Z
< I00

.~ BO - MANGANOUS
z
,<
60
m
~ 40

z 20
W

W
o ~- z q I I
~" I I z I I
I00 -

80-- MnO2 CONDITIONED WITH

HYDROXAMATE AT pH 9

4O

20-
0 I I I I I
4000 3000 2000 1600 1200 800
WAVE NUMBER, MICRONS
Fig. 7. Infrared spectra of potassium octyl hydroxamate and manganese dioxide condi-
tion with water; manganous octyl hydroxamate; and manganese dioxide conditioned
with the hydroxamate at pH 9.

Fig. 5. The effect of temperature o n the uptake of hydroxamate on 7-MnO 2.

Fig. 6. The effect of pH and hydroxamate concentration on the electrophoretic mobility

of-/-MnO2 in 2 × 1 0 - 3 M potassium nitrate; the electrophoretic behavior of precipitated
manganous hydroxamate.
148

I l I 1 t I I
MnO 2
I-- • 3x 10-4M HXm
z I00 I- 0 2 xlO-4 M & A
I o ,~ ,o-'M /, \
/ ~ 8,,o'~ / \
-

~> 6 0

~ 40 -

0 2 46 8 I0 12
pH
Fig. 8. The effect of pH on the flotation response of 7-MnO 2 at various additions of pot-
assium octyl hydroxamate.

I i I I I I

~" - M n O 2
Pz IOOi i'-I 10-6 M SOS
Z~ 10-5 -
0 I0 "4
o. 80

o 60

40

201

o! 2 4 l; -
pH
8 - I0 12

Fig. 9. The effect of pH on the flotation response of 7-MnO~ at various additions of

sodium dodecyl sulfonate.
 149

The flotation response of manganese dioxide with KXm as collector at

various pH's was investigated and the results summarized in Fig. 8. Since the
total surface area of the manganese dioxide used in each flotation experi-
ment was low, the added hydroxamate concentration approximates the
residual equilibrium concentration. Clearly, flotation recovery increases at
higher concentrations of hydroxamate, with a maximum at pH 9. At a col-
lector concentration of 3 × 10-4 M, all of the material floated. These condi-
tions correspond to monolayer coverage of hydroxamate on the surface of
the solid.
To show the flotation behavior with an anionic collector that only absorbs
physically as a counter ion in the double layer, flotation experiments were
also carried out with sodium dodecyl sulfonate (SDS) as the collector. Figure
9 summarizes the flotation response as a function of pH at various SDS con-
centrations.

DISCUSSION OF R E S U L T S

The PZC of this sample of manganese dioxide occurs at pH 5.6. As can be

seen by the results given in Fig. 9, sulfonate ions function as a flotation col-
lector essentially only when the manganese dioxide surface is positively
charged, that is at pH's less than the PZC. Thus, flotation with the sulfonate
collector occurs essentially through adsorption of the collector anion onto
the positive surface. On the other hand, since there is no adsorption or flota-
tion with hydroxamate in this pH range, the adsorption process for hydroxa-
mate must be mainly chemical in nature. Furthermore, a peak in both ad-
sorption density and flotation recovery occurs at about pH 9, a pH at which
the manganese dioxide surface must carry a high negative charge. Both the
adsorption density and flotation recovery increase gradually with increasing
pH until about pH 9, and then drop rather sharply at higher pH's. Since the
reported value of the PKa of hydroxamate is around pH 9, one might con-
clude that the aqueous chemistry of hydroxamic acid may be of importance
in adsorption and flotation.
The question is whether adsorption occurs through specific adsorption of
hydroxamate anions, hydroxamic molecules, or a combination of both. Rela-
tive to the adsorption maximum, the decrease in adsorption is very minimal
as the pH is lowered from 9 to 5, in contrast to the hundred-fold change
generally observed in an ionic surfactant system over a narrow pH range
(Somasundaran and Fuerstenau, 1966). As can be seen from Fig. 4, adsorp-
tion of hydroxamate increases as the pH is increased above the PZC of
manganese dioxide, similar to the behavior observed on ferric oxide (Rag-
havan and Fuerstenau, 1975). Under these conditions, the fraction of hy-
droxamate that is ionized is increasing while at the same time the charge on
the surface is becoming more negative. Below pH 9, unionized hydroxamic
acid is the predominant species, whereas above pH 9 hydroxamate anions
dominate. This repelling of hydroxamate anions by the negative surface
150

charge could account for the sharp decrease in adsorption above pH 9. Our
opinion is that the dominant species acting in the adsorption process must be
hydroxamic acid molecules, but perhaps with coadsorption of hydroxamate
ions.
Since the PZC of this manganese dioxide occurs about pH 5.6, all other
observed reversals of the electrophoretic mobility are isoelectric points -- or
points of zeta potential reversal (PZR) and not points-of-zero-charge (PZC).
The electrokinetic results indicate a shift in the IEP (that is the value of the
zeta potential is more negative at any given pH) due to chemisorption. If the
adsorption process is one involving the adsorption of both hydroxamate
molecules and hydroxamate ions, strong specific adsorption of the ions
could account for the increase in the negative value of the zeta potential.
Interestingly enough, a shift in the IEP still occurs, even though it is far be-
low the PKa of hydroxamate, where most of the hydroxamate added will be
in the form of the hydroxamic acid species. Another contribution to the ob-
served shift in pH of the IEP may be due to the acidic nature of the N-H
group in hydroxamic acid (Raghavan and Fuerstenau, 1975). Possibly the
surface chelate formed through specific interaction of the hydroxamic acid
species with the manganese dioxide surface ionizes, leaving a negative charge,
as indicated by the highly negative charge of precipitated manganous hy-
droxamate (Fig. 6).
The infrared spectra of manganese dioxide conditioned with water shows
a broad hydroxyl band at 3450 cm-1 corresponding to the OH-stretching
mode. The spectra of octyl hydroxamate has a broad band at 1650 cm -1 cor-
responding to the amide I band (C=0 stretching), 1570 cm-1 (amide II band),
1000 cm-1 (C-H out of plane vibration) and 980 cm -1 (N-O stretching). The
spectrum of manganous hydroxamate precipitated from aqueous solution
has a principal band at 1600 cm -1, presumably corresponding to the C+O
stretching frequency. This decrease in the wave number is due to coordinate
covalent bond formed by the carbonyl oxygen with the manganese atom.
The IR spectrum of manganese dioxide conditioned at pH 9 with octyl hy-
droxamate clearly exhibits a peak at 1600 cm -1, indicating the presence of
manganous hydroxamate chelate at the surface. Furthermore, the surface
hydroxyl band on managese dioxide has disappeared upon conditioning
with hydroxamate. This also would support the postulate that the hydrox-
amic acid molecule is the actively adsorbing species, perhaps by the follow-
ing mechanism:
t t
t O=C-R I O=C-R
'Mn-OH + ] ~ ~'Mn ~ ] + H20
t HO-N-H J ~ O-N-H
I I

Palmer et al. (1975) observed that rhodonite (MnSiO3) flotation occurs in

the pH range in which Mn** hydrolyzes to MnOH ÷. They expressed the opin-
ion that it is the surface character of manganese that is responsible for ad-
 151

sorption. Utilizing bulk solution equilibria, they postulated that mineral dis-
solution and metal ion hydrolysis in the bulk solution are intimately in-
volved in the adsorption process. If some of the surface manganese on man-
ganese dioxide is M n +~, the peak observed in this investigation might also be
due in part, to the presence of hydroxylated species on the surface.
The adsorption density at room temperature (22°C) in the p H range of 8
to 9 was found to firstreach and then exceed a monolayer as the bulk con-
centration of hydroxamate is increased. This could result from the physical
adsorption of hydroxarnate on top of the surface chelate or could be due to
the surface precipitation of basic manganous hydroxarnate. The formation of
a brown colloidal solution was observed while conducting adsorption and
flotation experiments at p H values above 9, which most likely is manganous
hydroxamate precipitate. Similar phenomena were observed by Raghavan
and Fuerstenau (1975) and Palmer et al. (1975).
In most aqueous chemisorbing systems, an increase in temperature en-
hances adsorption, and the adsorption density in this system was also ob-
served to increase with increasing temperature. Since an increase in tempera-
ture should reduce adsorption density for exothermic processes (Raghavan
and Fuerstenau, 1976), this suggests that the adsorption of hydroxamate on
manganese dioxide is endothermic. However, the increased adsorption at
higher temperature m a y actually be due to increased dissolution of the man-
ganous species, forming positively charged M n O H ÷ which are likely to inter-
act with either the hydroxamic acid species or the hydroxamate anions and
form the basic manganous hydroxamates.
For a Langmuir-type adsorption isotherm, surface coverage can be related
to the equilibrium concentration in solution by the following equation:

1-0 - 55.5 exp \ RT

where 0 is the fraction of the surface covered by the adsorbate, C is the con-
centration of the adsorbate in solution (mole/liter) and AG°a& is the stan-
dard free energy of adsorption. Considering hydroxamic acid as the adsorb-
ing species, AG°ads was calculated and found to be of the order of - 3 4
kjoule/mole, similar to the value for the standard adsorption free energy re-
ported by Raghavan and Fuerstenau (1975) for the HXm-hematite system. The
constancy of the AGads alSO lends support to the postulate that hydroxamic
acid molecules are the reactive species in adsorption and flotation.

SUMMARY A N D CONCLUSIONS

Phenomena associated with the interaction of potassium octyl hydroxa-

mate with manganese dioxide were investigated through measurements of
adsorption densities, electrokinetic behavior, infrared absorbance, and flo-
tation response. The most pronounced adsorption and flotation effects in
this system occur at pH's above the PZC of manganese dioxide, which was
152

found to occur at pH 5.6. Maxima in adsorption and flotation response were

observed at about pH 9, the pK a of hydroxamic acid. The active adsorbing
species appears to be hydroxamic acid molecules that interact with manga-
nese ions in the surface, displacing surface hydroxyls to form manganese
hydroxamate. The maximum in flotation at pH 9 may result from coadsorp-
tion of hydroxamic acid molecules and hydroxamic ions. The decrease at
higher pH's results from repulsion of hydroxamate ions by the highly nega-
tively charged manganese oxide. At room temperature and lower concen-
trations, the adsorption density tends to monolayer coverage; but at higher
concentrations there is multilayer coverage, apparently due to physical ad-
sorption onto the chemisorbed layer of surface-chelated hydroxamate. Ad-
sorption increases with increasing temperature, and this may result from
both the endothermic nature of the process and from increased solubility
of the mineral. The flotation response of manganese dioxide with a sulfonate
collector clearly illustrates the relatively simple adsorption behavior of physi-
cally adsorbing collectors, and particularly the role of surface charge in the
collection process.

ACKNOWLEDGEMENTS

One of the authors (R.N.) gratefully acknowledges the International

Atomic Energy Agency, Vienna, for the award of a Technical Assistance
Program Fellowship during the course of this investigation. Partial support
of this research by the National Science Foundation is also acknowledged.
The supply of electrolytic manganese dioxide by the Union Carbide Corpo-
ration, Parma, Ohio, is appreciated.

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York, N.Y.
Bhaduri, A.S., 1956. Salicylhydroxamic acid as an analytical reagent, Part I -- gravimetric
estimation of cadmium, uranium and vanadium. Z. Anal. Chem., 151: 109--118.
Brenet, J.P., 1962. Batteries, 3. Pergamon Press,N e w York, N.Y.
DeWitt, C.C. and van Batchelder, F., 1939. Chelate compounds as flotation reagents. J.
A m . Chem. Soc., 61: 1247--1250.
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tion. In: M.C. Fuerstenau (Editor), Flotation, Gaudin Memorial Volume. Chapter 3:
21--65.
Fuerstenau, D.W., Metzger, P.H. and Seele, G.D., 1957. Modified Hallimond tube for
flotation testing. Eng. Min. J., 158: 93--95.
Fuerstenau, M.C. and Rice, D.A., 1968. Flotation characteristics of pyrolusite. A I M E
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Fuerstenau, M.C., Harper, R.W. and Miller, J.D., 1970. Hydroxamate vs. fatty acid flota-
tion of iron oxide. AIME Trans., 247: 69--72.
 153

Gutzeit, G., 1946. Chelate-forming organic compounds as flotation reagents. ALME

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