International Journal of Mineral Processing 98 (2011) 48–54

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International Journal of Mineral Processing

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / i j m i n p r o

Flotation kinetics of a pyritic gold ore

E. Yalcin a, S. Kelebek b,⁎
a
Hemlo Mines-Williams Processing Plant, Barrick Gold Corp., P.O. Bags 500, Marathon, Ontario, Canada P0T 2E0
b
The Robert M. Buchan Department of Mining, Queen's University, Goodwin Hall, Kingston, Ontario, Canada K7L 3N6

a r t i c l e i n f o a b s t r a c t

Article history: Kinetics of semi-batch flotation behavior of a gold ore from North-Western Quebec, Canada was investigated with
Received 9 June 2010 respect to fineness of grind (P80). The gold was mostly associated with pyrite in native form as inclusions and was
Received in revised form 11 October 2010 also in contact with pyrite along the boundaries of non-sulphide gangue. Gold recoveries were found to increase
Accepted 16 October 2010
from 91.8% to 95.8% as the particles size decreased from an F80 of 205 μm to 53 μm. Data treatment according to
Available online 19 November 2010
the graphical method of kinetic analysis indicated a much better fit to second order kinetics for both gold and
Keywords:
pyrite with correlation coefficients higher than 0.998 compared to first order kinetics with correlation coefficients
Gold ore flotation of less than 0.95. Variation and implication of flotation rate constants are discussed with respect to chemical
Pyrite flotation conditions and particle size.
Flotation kinetics © 2010 Elsevier B.V. All rights reserved.
PAX
IPX
Particle size

1. Introduction behaviour to a greater extent especially when they experience a mild

In general, liberated native gold is recovered by gravity methods as
long as particle size is not too small. However, in the majority of cases,
gold is in an extremely fine state and usually in the form of solid solution
inclusions. The gold can be at a highly concentrated level in some
sulphides such as pyrite and arsenopyrite (Petruk, 2000). Since such
ores may be refractory to chemical processing by cyanide leaching,
flotation is a favourable option as an integral step in gold extraction.
Flotation as a physico-chemical process is a mature technology that
has been practiced successfully for more than a century. In contrast to
the case for flotation characteristic of base metal bearing ores, there is a
very limited amount of research work reported on flotation of gold ores.
Flotation rate of gold varies significantly depending on its geological
origin, composition and the environment in which it is present. For
example, Nagaraj et al. (1992) demonstrated that presence of silver in
gold in the form of an alloy (known as electrum) is highly critical for
selective adsorption of di-p-cresyl monothiophosphate as a collector
and is effective for its flotation. Under ordinary conditions of processing,
elemental gold has been observed to float by itself, with no addition of a
specific collector. Allan and Woodcock (2001) in their review attracted
attention to some observations on native gold particles skin-floating on
the surface of a pulp as a loss to the tailing from sluice boxes, which date
back to the 1910–1920 period, the era generally coinciding with infancy
of the flotation process. The sulphide minerals exhibit the same
⁎ Corresponding author. Tel.: +1 613 533 2207; fax: +1 613 533 6597.
E-mail address: kelebek-s@mine.queensu.ca (S. Kelebek).
oxidation causing sulphur enrichment at their surfaces, which promote
their floatability without any collector addition (Heyes and Trahar,
1977; Kelebek and Huls, 1991). Fundamental research work indicated
that a pure gold surface is hydrophilic in its clean original surface state
(Gardner and Woods, 1977). It seems that numerous impurities found
in the natural environment containing native gold are attracted to this
noble metal. As far as flotation reagents are concerned, Wang and Yoon
(2009) studied the attractive force between gold surfaces in xanthate
solutions using surface force measurements. The attractive force
developed by adsorption of xanthate was pointed out to decrease
with aging and increase with the concentration of the xanthate.
The majority of the developments on flotation of gold and gold
bearing ores were summarized in recent reviews (O'Connors and
Dunne, 1994; Allan and Woodcock, 2001; Dunne, 2005). These focused
on mineralogical characteristics, application of reagents and their
interactions in flotation as well as the processing flowsheets. Presence
of excess amount of slimes has a negative effect on gold flotation
recovery. Likewise, an excess amount of collector is considered to be
detrimental to the recovery. In general, the range of applicability of
flotation is considered to cover gold particles from about 200 μm flakes
to 1 μm particles. Relatively large gold particles float more slowly than
the intermediate to fine particles. Collector addition in stages has been
shown to improve flotation of native gold especially that of relatively
coarse flaky particles (Chryssoulis et al., 2003). Review of the literature
above indicates that virtually no data were reported on kinetic aspects of
gold flotation. The current work presents a study on flotation rate of a
pyritic gold ore with respect to fineness of grind size.

0301-7516/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2010.10.005
 E. Yalcin, S. Kelebek / International Journal of Mineral Processing 98 (2011) 48–54 49

2. Experimental Table 1
Chemical analysis of ore sample.

2.1. Ore sample and mineralogy Component Assay

Gold 5.18 g/tonne

The sample studied was an auriferous ore originating from the Barry
Region in North-Western Quebec, Canada. Basic characterization work
undertaken on samples from this ore deposit (Lariviere, 1997) indicated
that gold mineralization occurs within albite-carbonate-quartz veins and
the surrounding carbonate-quartz-pyrite and locally biotite-carbonate
alteration zones of the host mafic volcanic rocks. Gold is present within
pyrite (and other sulphides such as pyrrhotite in minor quantity) as well
as along microfractures in pyrite or in contact with pyrite grains, less
abundantly with pyrrhotite. Some photomicrographs are shown in Fig. 1,
which indicates major modes of occurrence of native gold in the sample
studied. Table 1 shows analytical results obtained on the head samples for
the ore sample tested. Analysis of gold was carried out by fire assay
followed by an atomic absorption spectrophotometer (Perkin Elmer,
Model 2380) that was also used for determination of iron. The amount of
total sulphur and carbon was determined using LECO (Carbon and Dual
Range Sulphur Analyzer, Model SC-444DR). The methods involved the use
of appropriate amounts of standards, namely zinc sulphide (32.52% S) and
Calcite (12.0% C).
2.2. Crushing and charge preparation
The ore sample was crushed in a laboratory jaw crusher, followed by
a gyratory crusher, and a roll crusher that was run in a closed circuit with
a 10 mesh Sweco screen. Screen undersize product obtained was
blended and split into separate charges weighing about 1000 kg using a
Iron 6.67%
Sulphur 0.81%
Carbon 2.41%
rotary splitter with an adjustable speed vibratory feeder. All charges
were kept in a deep freezer until they are required for flotation testing.
2.3. Grinding and classification tests
The grinding mill used in this work was a laboratory scale rod mill
from Denver Equipment. The grinding media consisted of about 14 kg
rods, which were made up in four different diameters. The mill interior
had five lifters by design to facilitate tumbling action for grinding. The
grinding mill was of mild steel. Grinding media typically was of stainless
and mild steel (at 50–50 mixture). The samples were ground at about
67% solids by weight with local tap water for various periods to produce
test feeds with varying fineness of grind, which was differentiated by the
P80 values (i.e., 80% cumulative passing size). For this purpose, the
ground samples were subjected to standard screening tests using a
series of laboratory sieves (The W.S. Tyler Company of Canada Ltd.,
St. Catharines, ON). The screens used were from 635 mesh (20 microm-
eter in aperture) up to 35 mesh (425 micrometer in aperture). The data
were then used to establish a “grind curve” for the mill used. In order to
simulate the mill practice, the pH regulator was added into the grinding

Fig. 1. Photomicrographs of the mode of occurrence of gold at the Barry deposit. (A) Photomicrograph of free gold grain in siliceous gangue and pyrite (grey areas are finely disseminated
illmenite and magnetite). The photo on the right is a close up view of the same gold grain (50 μm), (B) Photomicrograph of gold occurring in contact with pyrite as free gold in gangue and
strong biotite alteration. The photo on the right (b) is a close up view of the 10 gold grains of 1–10 μm (Lariviere, 1997).
50 E. Yalcin, S. Kelebek / International Journal of Mineral Processing 98 (2011) 48–54
mill for each test. The transfer of slurry into the cell for each test was kept
constant at 5 min.
2.4. Reagents
The pH regulator used in grinding at a single dosage was soda ash.
The collector used in flotation tests was a mixture of two xanthates,
namely PAX (i.e., potassium amyl xanthate) and SIPX (sodium isopropyl
xanthate). Before use in the experimental program, both xanthates were
purified according to standard procedures in the literature (Rao, 1971)
and kept under petroleum ether in a dark glass bottle. When needed, an
appropriate amount of xanthate was pipetted out onto a watch glass to
allow evaporation of the ether in a fume hood, then weighed and
dissolved in deionized water to prepare a fresh aqueous solution at 0.1%
wt strength. Frother was MIBC (methyl iso butyl carbinol), which was
used at its full strength in the form of droplets. One third of xanthate was
added at the grinding stage. The remaining dosage of xanthates and
MIBC was equally distributed before each stage. The overall dosage
levels of the reagents are shown in Table 2.
2.5. Flotation tests
Batch tests were carried out using standard Denver laboratory rod
mill and Denver flotation machine with a 2-L cell. With the amount of
ore used, the pulp density of the flotation feed became about 38% solids
by weight. Following the grinding using 300 g/tonne of soda ash the
flotation feed had an initial pH of 8.7 to 9.0. No new addition of soda ash
was made during flotation. Pulp pH levels were monitored during each
test using a portable unit (model 3000) from VWR Scientific, which was
equipped with a combination electrode and probe for temperature
compensation.
Flotation gas rate was based on the natural suction of air into pulp
through the shaft of impeller set at 1200 rpm. Total flotation time was
fixed at 7 min. A total of four concentrates were skimmed off at 0.5, 1.5, 2
and 3 min with a froth removal frequency of 30 strokes per minute.
Solid products from all separation tests were dried and weighed for
the construction of mass balance tables. Analyses of gold in all products
were carried out using the fire assay procedure developed for sulphur
bearing ores. In cases where the amount of solids was insufficient for an
assay ton (i.e., 29.17 g), a concentrate sample was pre-diluted with a gold-
free granite sample, which was taken into account in mass balancing.
3. Results and discussion
3.1. Interaction of xanthates with gold and pyrite
Xanthates are common surfactants used as collectors in flotation
recovery of pyrite and other sulphides that are associated with gold.
Interaction of xanthates and gold and pyrite has a strong electrochem-
ical basis that involves adsorption of xanthate for the formation of a
hydrophobic layer as a first step to be followed by formation of
dixanthogen (X2) as an outer hydrophobic layer that is even stronger
than the initial adsorbed xanthate layer.
−
X ↔ Xads + e ð1Þ
−
Xads + X ↔ X2ads + e ð2Þ
The chemisorption results in formation of a hydrophobic surface
product on gold and iron-bearing species. In a recent study of cycling
voltammetry and surface force measurements with gold treated with
potassium amyl xanthate (Wang and Yoon, 2009), hydrophobicity of
gold reached a maximum level corresponding to a contact angle of 94°,
which was attributed to formation of di-amyl dixanthogen on top of the
chemisorbed layer of amyl xanthate. Solubility products for the
interaction of gold with various xanthates are given by Kakovsky
(1957). The following can be written for formation of gold ethyl
xanthate:
þ − 29
Au + X ↔ AuXs K = 1:67*10 ð3Þ
The interaction of xanthates with iron species is of interest with
respect to flotation of pyrite. The chemical interaction between ferrous
iron and ethyl xanthate has a much smaller stability constant
(Kakovsky, 1957):
2 + − 7
Fe + 2X ↔ FeðX2 Þs K = 1:58*10 ð4Þ
Interaction of ferric iron species is more important since flotation
often takes place in an oxidizing environment. Critchley and Hunter
(1986) reported the solubility products of several ferrix xanthates,
based on which the following is valid for ferric ethyl xanthate:
3 + − 24
Fe + 3X ↔ FeðX3 Þs K = 6:31*10 ð5Þ
It can be seen that reactivity of xanthate with gold particles has a
stronger thermodynamic driving force compared to iron species. Since
pyrite flotation is practiced in alkaline slurries, the interaction of
hydroxylated ferric species with xanthates is also important. For
example, in an alkaline medium applicable to flotation circuits, a ferric
dihydroxy ethyl xanthate can form.
3 + − − 34
Fe + 2OH + X ↔ FeðOHÞ2 Xs K = 3:98*10 ð6Þ
Corresponding K value for the ferric dihydroxy amyl xanthate is
3.98 × 1034. Dixanthogen formation on top of such a hydroxy xanthate
layer on pyrite is also chiefly responsible for the hydrophobicity and
floatability of this mineral (Wang and Forssberg, 1991).
It can be concluded from above that the flotation mechanisms of gold
and pyrite with xanthates have important common features. Branched
xanthates are considered to be somewhat better suited for development
of hydrophobicity than the straight chain xanthates, and joint action of
two collectors (adopted in the present work) is generally recognized to
be more efficient (Klassen and Mokrousov, 1963). The latter aspect has
been demonstrated for a collector mixture of PAX and di-isobutyl
dithiophosphate in gold flotation through a surface analytical technique
(Chryssoulis and Dimov, 2004).
3.2. Flotation recovery as a function of time
Flotation recoveries of gold obtained are shown in Fig. 2 as a function of
time, which indicates recoveries between 91.8% and 95.8% within 7 min
depending on the grind size (P80). These results have been obtained using
a fixed dosage of soda ash to provide a pH of around 9 that is known to
allow high recoveries for both gold and pyrite unless the latter is heavily
oxidized (Monte et al., 2000). Mass recoveries are also given in this figure.
In general, such a low mass recovery is attributable to a low level of
sulphides in the ore corresponding to about 0.8% (Table 1) as well as the
strong selectivity of xanthates against the non-sulphide components. The
flotation test at a P80 of 205 μm yielded a mass recovery of about 3.66%,
and corresponded to a gold recovery of 91.8%. This lower recovery may in
general be attributed to floatability problems of coarse particles. The
floatability by particle size curves for sulphides indicate significant drops
around 200 μm (Trahar, 1981). However, considering that gold is 4–5
times heavier than a sulphide-bearing mineral, a greater decrease in gold
recovery would be expected at this grind size. That the recovery has not
dropped more significantly is indicative of a strong possibility that the
gold particles after grinding are mostly recovered together with the pyrite
component of the ore. Another point is that the samples used contain an
insignificant amount of liberated native gold particles that were too coarse
for the recovery to drop more drastically. In order to examine the first
point, pyrite content of the flotation products were estimated from the
 E. Yalcin, S. Kelebek / International Journal of Mineral Processing 98 (2011) 48–54 51

100 6 Table 2
Reagents used in testwork.

90 Reagents Dosage (g/tone)

5
Soda ash (pH 8.8–9.0) 300
Potassium amyl xanthate (PAX) 55

Mass Recovery (%)

Gold Recovery (%)

80 Sodium iso-propyl xanthate (SIPX) 55

4 MIBC 50

70

3 in which C is the concentration of particles in the flotation cell, t is

60
Au Rec. Mass Rec.
50
40
0 1 2 3 4 5
Flotation Time (minutes)
Fig. 2. Flotation recovery of gold as a function of time at different fineness of grind and
corresponding mass recoveries.
sulphur assays. For this purpose, the products were assayed for copper,
lead and zinc assays to subtract their share of sulphur from the overall
sulphur. As it turned out, only a minor adjustment was needed for copper
that was present at 0.2–0.3% level only in the first two concentrates. In this
ore, the percentage of base metals other than iron was too low
(~0.01% wt.) to significantly affect the pyrite balance. Fig. 3 shows a plot
of gold recoveries versus calculated pyrite recoveries. As may be noted,
despite some scatter, the gold recoveries follow a 1:1 relationship with
pyrite. Mineralogical investigations (Lariviere, 1997) also support this
view by drawing attention to close association of native gold with pyrite.
The gold grains are substantially smaller than pyrite grains (Fig. 1). The
gold recoveries show systematic increases to 92.4%, 94.4% and 95.8%,
when the P80 values have been reduced to 159 μm, 92 μm and further to
53 μm, respectively. An incremental increase in gold recovery is
attributable to improved liberation with finer particle size.
3.3. First order kinetics
The flotation data plotted in Fig. 2 have been examined from a
kinetics point of view. Flotation kinetics can be studied by analogy to
chemical kinetics. The rate equation in its simple form may be written as
n
dC =dt = −kn C
100
time, k is the flotation rate constant and n is an integer determining
the order of the rate equation. The rate constant is dependent on a
P80: 53 µm
number of variables, some related to ore characteristics such as
P80: 92 µm 2
mineralogy, particle size and surface chemistry, others to operating
P80: 159 µm
variables such as dosage of reagents and degree of aeration.
P80: 205 µm
Eq. (1), when integrated for the first order flotation kinetics
1 (Arbiter and Harris, 1962) respectively leads to
6 7 8
−k1t
R = R∞ ð1 – e Þ ð8Þ
where R is the cumulative recovery after time t and R∞ is the
maximum recovery after prolonged flotation time and k1 is the first
order rate constant.
In general, concentration of valuable minerals through capture of
particles by bubbles in flotation is considered to follow the first order
kinetics. Therefore, this model has been considered as the first case.
Rearranging Eq. (8) results in the following linear form:
Ln ½ðR∞ − RÞ = R∞  = − k1 t ð9Þ
If the first order model is valid, a plot of the left hand side of Eq. (9) as a
function of time should result in a straight line. The experimental data are
accordingly plotted in Fig. 4 for the four particle sizes studied. Kinetic
parameters obtained from this analysis are given in Table 3 with overall
recoveries corresponding to each case. As may be noted, results depend on
the maximum recovery values adopted. The filled symbols (a) denote the
calculated results based on the R∞ values adopted in the vicinity of plateau
for each case reported in Fig. 2. Correlation coefficients from linear
regression show two distinct groups, one lower than the other. The lower
group of data was obtained by using higher R∞ values by extrapolation to
larger values based on second order kinetics to be discussed below. This
second set indicated a distinct curvature (b) in Fig. 4. Regardless of what
the values of R∞ are, a deviation from linearity is significant. In general, the
flotation rate constant decreases with increasing particle size. However, in
the size range investigated, the particle size dependence of the rate
ð7Þ

90
Au Recovery (%)

80

70

60
P80: 53 µm
P80: 92 µm
50
P80: 159 µm
P80: 205 µm
40
40 50 60 70 80 90 100
Pyrite Recovery (%)
Fig. 4. Experimental data plotted according to 1st order flotation kinetics (using two R∞
Fig. 3. Gold recoveries versus estimated pyrite recoveries. values, a and b explained in the text).
52 E. Yalcin, S. Kelebek / International Journal of Mineral Processing 98 (2011) 48–54

Table 3 8.0
Parameters for the first order flotation kinetics of gold in the sample used. P80: 53 µm
7.0 P80: 92 µm
2 2
P80 Rovr R∞ (a) k1 r R∞ (b) k1 r
(μm) (%) (%) (min−1) (%) (min−1) P80: 159 µm
6.0
P80: 205 µm
53 95.8 95.9 1.07 0.9498 98.4 0.64 0.5779
92 94.4 94.5 1.03 0.9399 97.1 0.63 0.5772 5.0
159 92.4 92.5 1.06 0.9447 95.6 0.61 0.5633

t/R
205 91.8 92.0 0.96 0.9400 95.6 0.57 0.6015
4.0

constant for the sample tested appears to be strikingly small. One factor for
this might be related to a liberal dosage of collector used compared to
some other studies on gold flotation (Chryssoulis et al., 2003). In general, a
high dosage of collector tends to even out floatability of particles with
respect to their size (Torem et al., 2006). This is presumably related to
improvement of the recovery of coarse particles that are known to be
highly sensitive to collector concentration (Trahar, 1981). Industrial
practice on recovery of precious metals tends to use higher dosages in lieu
of "insurance" given the relatively small cost of reagent. Another factor for
this behavior may be related to use of mixed xanthates, i.e., normal chain,
PAX and branched chain, SIPX, and perhaps more importantly, 30% of their
addition into the grinding mill, where soda ash has been used as the pH
regulator during size reduction. Grinding with soda ash as a pH regulator
is beneficial to promote bulk flotation since lime as an alternate is known
to have some detrimental effect on flotation of pyrite (Gaudin, 1957;
Klassen and Mokrousov, 1963) and gold (Dunne, 2005). Use of lime
increases the concentration of calcium ions in the flotation slurry, which
tend to block active sites for collector. In contrast, soda ash can act as a
dispersant (hence helpful for selectivity against gangue) and is able to
combat adverse effect of excess calcium ions by causing their precipita-
tion, which, by itself, might cause a problem in some cases. A detailed
bench scale comparison on the effects of soda ash and lime is reported
elsewhere (Kelebek, 2009). First order kinetic analysis was also carried out
for pyrite. Results are summarized in Table 4, which indicate similar trends
to the case reported for gold (Table 3). However, although the rate
constants are of the same order of magnitude, there are some
inconsistencies, e.g., the rate constant for P80 of 159 μm in the first series
(k1 = 0.78 min−1) is significantly smaller than that of 205 μm
(k1 =1.16 min−1). In the second series, the rate constants are the same
for the smaller two (0.68 min−1) and for the larger two grind sizes
(0.58 min−1), which makes validity of the first order kinetics for this
sample questionable.
3.4. Second order kinetics
Since treatment of data according to the first order kinetics has
resulted in a significant degree of scatter and apparent inconsistencies,
applicability of the data for second order flotation kinetics needed to be
tested. Eq. (7), when integrated for the second order flotation kinetics
respectively yields the following (Arbiter and Harris, 1962):
R∞2 k2 t
R¼
1 + R∞ k 2 t
3.0
2.0
1.0
0.0
0 1 2 3 4 5 6 7 8
Flotation Time, t (minutes)
Fig. 5. Experimental data plotted according to 2nd order flotation kinetics.
where k2 is the second order rate constant. Re-arranging Eq. (10) one
can get
t t 1
= + 2 ð11Þ
R R∞ R∞ k2
If the second order equation is valid, a plot of “t/R, flotation time/
recovery” against time t (cumulatively for both cases) should result in a
straight line. The results plotted accordingly are shown in Fig. 5. As may
be noted, the same data now result in a very good linearity as compared
with the results of the first order kinetics (Fig. 4). The R∞ values obtained
from slopes and second order rate constants, k2 obtained from the
intercept values for each case are tabulated in Table 5. The correlation
coefficient (r2) obtained for each case is greater than 0.999 compared to
0.949 or less for the first order case (Table 3). Due to this excellent data
fit, the alternate ultimate recoveries for the first order kinetics (i.e., R∞(2)
in Table 3) were the R∞ values obtained from the second order model
(Table 5) demonstrating sensitivity of k1 and r2 values to variation in the
R∞ values. The second order rate constants, k2 appear to vary more
systematically with respect to particle size. The second order flotation
kinetic parameters were also computed for the pyrite component of the
ore sample studied. These results are given in Table 6. Model fit of the
pyrite data to second order kinetics is also much better than to that of
first order kinetics. It is interesting that the recovery of pyrite at smaller
grind sizes (i.e., P80 53–92 μm) is consistently lower than that of gold.
However, the second order flotation rate constants for pyrite at these
grind sizes are significantly higher than those for gold. In fact, this trend
may also be noted from a comparison of their first order rate constants
(Tables 3 and 4), although the difference is somewhat smaller in this
particular case. Despite higher rate constants, the overall recoveries of
pyrite are somewhat lower than those of gold. This can be related to
oxidizable nature of sulphides. Data by Monte et al. (2000) show that
ð10Þ flotation of oxidized pyrite in the alkaline pH range goes down
significantly compared to both gold and fresh pyrite. A similar behavior
was found for oxidized pentlandite in samples from aged ore stockpile
(Kelebek and Nanthakumar, 2007).

Table 4
Parameters for the first order flotation kinetics of pyrite in the sample used. Table 5
Parameters for the second order flotation kinetics of gold in the sample used.
P80 Rovr R∞ (1) k1 r2 R∞ (2) k1 r2
(μm) (%) (%) (min−1) (%) (min−1) P80 (μm) Rovr (%) R∞ (1) (%) k2 (g−1 min−1) r2

53 94.8 94.9 1.23 0.9296 97.0 0.68 0.5180 53 95.8 98.4 5.61 0.9996
92 94.1 94.2 1.15 0.9317 96.3 0.68 0.5044 92 94.4 97.1 5.41 0.9999
159 92.3 92.3 0.78 0.7599 95.8 0.58 0.5825 159 92.4 95.6 4.89 0.9997
205 91.8 91.8 1.16 0.9392 95.8 0.58 0.5130 205 91.8 95.6 4.07 0.9999
 E. Yalcin, S. Kelebek / International Journal of Mineral Processing 98 (2011) 48–54
Table 6
Parameters for the second order flotation kinetics of pyrite in the sample used.
P80 (μm) Rovr (%) R∞ (1) (%) k2 (g−1 min−1)
53 94.8 97.0 7.09
92 94.1 96.3 7.20
159 92.3 95.8 4.55
205 91.8 95.8 4.11
The variation of flotation rate constants with respect to grind size is
graphically shown in Fig. 6. As can be noted, the first order rate constants
are nearly independent of particle size compared to the case with the
second order kinetics. Although use of a relatively high dosage of mixed
collectors may have had a role in this small dependence of flotation rate
on grind size, extent to which this happens, does not appear to be in
agreement with trends of flotation recovery by particle size (Trahar,
1981), which suggest that flotation rates should be lower as the particle
size approaches 200 μm under conditions of current work. In contrast,
the second order flotation rate constants obtained show a greater
relative dependence on fineness of grind, which is to be expected based
on analysis of recovery by size data. Greater second order rate constants
for pyrite at grind sizes of P80 of 53 and 92 μm are compatible with highly
floatable behavior of sulphides at such intermediate sizes. The
comparatively lower second order rate constants that were obtained
for gold in this size range imply that part of the gold grains might be
behaving independent of pyrite particles. This is possible in view of the
mineralogical characteristics which have indicated presence of much
finer gold grains (e.g., 10 μm or even lower) that are in contact with the
pyrite surface at boundaries with non-sulphide gangue as documented
in Fig. 1B/b. These fine particles can detach from the surface of pyrite
grains in the grinding mill environment and flotation cell through
abrasion/attrition events. On this basis, a slower flotation rate of these
gold bearing fine particles is likely to have contributed to the lower
overall rate constants at the finer grind size range noted above. The
curves for second order rate constant tend to converge for the coarser
two grind sizes. This is interpreted as being a consequence of joint
recovery of pyrite and gold through flotation of their locked particles
(e.g., coarse pyrite particles containing finer gold mostly in embedded
forms, Fig. 1A/a).
3.5. Concluding remarks
In general, flotation recovery is considered to follow first order
kinetics. Many studies used the first order kinetics or its slightly
modified versions for various objectives (Agar and Barrett, 1983; Xu and
Stratton-Crawley, 1996; Kelebek and Nanthakumar, 2007). In a
Fig. 6. Variation of flotation rate constants with grind size.
53
comparative study (Hernainz and Calero, 2001) on flotation kinetics
of celestite and calcite, involving three models, i.e., first order, second
r2 order and a non-integral order model, second order model was
demonstrated to represent the data better than the first order model.
0.9999
0.9999 However, the non-integral model provided an even better fit to the
0.9997 flotation data with correlation coefficients reported in the range 0.91 to
0.9988 0.99. In a recent review on flotation fundamentals, Nguyen and Schulze
(2004) discussed the flotation kinetics and noted “flotation kinetics is in
general between first and second order, simplifying to first order for the
flotation of single minerals, or in dilute pulps, and to second order for
low grade ores or more concentrated pulps.” In the literature there are
very few studies that report second order kinetics for flotation. The
current work demonstrates one for recovery of both native gold and
pyrite from flotation of a pyritic gold ore under experimental conditions
detailed out, which indicated correlation coefficients of 0.998 or higher.
The second order rate constants have been found to better represent the
dependence of flotation rate on particle size.
Acknowledgements
The authors acknowledge the Natural Sciences and Engineering
Council of Canada (NSERC) for financial support. The authors are also
thankful to Dr. G. McIsaac for arranging the ore sample used and to
Mrs. M. Bailey for the laboratory assistance.
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