Adsorption and Flotation Studies with Quartz'

Part 11. The Adsorption of Laurate and Myristate on Quartz

S . M . AHMED' and A . B . VAN CLEAVE"

L'adsorption d'ions laureate et myristate sur du quartz

partir de solutions eontenant de
i 25 x
ionsg/litre de substance adsorbhe a dtd mesurde i diverses
valeurs de pH, aussi bien en prdsence qu'en I'absence d'ions
calcium, P I'aide de composds marquis au carbone 14.
Une eorrdlation a pu h e dtablie entre ces rdsultats et le
comportement du quartz cnvers la flottation ddtermind au
moyen d'un tube de Hallimond.

The adsorption of laurate and myristate ions on quartz

from solutions containing ( 1 to 25) x lo-' gm. ions/liter of
adsorbate at different pH values, both in the absence and
in the presence of Ca++ions, has been measured using C"labelled compounds as tracers. The results have been correlated with the flotation behavior of quartz as determined
by Hallimond tube and bubble pick up techniques.

c adsorption of calcium, hydrogen and hydroxyl ions on

T h quartz and the mechanism o f activation of quartz surfaces
for flotation have been the subject of a previous conimunication").
In the present work, an attempt has been made to measure the
adsorption of <?4-labelled lauratc or myristate ion on quartz,
both in the absence and in thc presence of <:a++ions, by measuring
the tracer activity in solution before and after adsorption. The
measurements are based on the principles discussed in Part I of
this scrics(l).

EXPERIMENTAL
The experimental methods and materials were the same as
used in Part I , except for the fcllowing:
Labelled samples of lauric acid-l-(?4 and myristic acid-I-C"
with a specific activity of 0.1 me. were obtained from .\toniic
Energy of Canada I d . Inactive samples of solid sodium laurate
and myristate were prepared by neutralizing an alcoholic solution
of the appropriate acid with NaOH. The purity of the original
acids was determined by a gas chromatographic method to be
as follows:
lauric acid; 0.9y0 n-decanoic
Laurie acid sample - 97. lyG
acid; 1 . 3 % niyristic acid; 0.7%
unidentified fatty acid.
Myristic acid sample - 88.7y0 myristic acid; S.O% lauric
acid; 6.3% palmitic acid.
For adsorption experiments, suitable amounts of the CL4-labellect
compound were added to inactive soap of the desired concentration in 6% ethanol in water solution. .\bout 3.6 gram samples
of quartz (total surface area approximatcly 1500 c111.*) were
used with 10 ml. samples of each test soluticin. l'hc exact
weight of dry quartz and the \\.eight of water adhering to thc
wet sample were determined separately. In experiments involving
Ca++ ions, the initial concentration of (:a++ ions in solution was
adjusted to maintain the same proportions of <:a++ ion to quartz
surface as reported in Part I, thus providing conditions under
which the proportion of rhe surface covered by (:a++ ions is
known. Polyethylene bottles of 25 ml. capacity were used as
containers in place of glass vials, In each series o f experiments
one sample bottle with no quartz present was used as a blank.
An amount of water equivalent to that adhering to the quartz
sample was weighed into this blank test before the C"-labelled
solution was added. Samples were shaken niechanically for
45 minutes; three aliquots of 2 ml. each of the solution were
then transferred to glass bottles of low potassium content.
These samples were evaporated to dryness on a water bath.

...............................................................................

'Manuscript received June 18 1963; accepted May 25, 1964.

'Deportment of Mines and TeLhnicd Surveys, M i w s Branch, Ottawa, Ont.
"Chairman, Dioisinn of Nafcrral Sciences, Unioersity of Saskatchewan,
Regina Campus, Regina, Sask.
Abstracted frmn the Ph.D. thesis of S. hf. Ahmed, University of Saskatchewan, Saskatoon, Sask., September 1962.

The Canadian Journal

of Chrmtical Engineering. Febrwry,

lo-'

Kach dry residue was dissolved in 5 nil. of9570 ethanol (prepared

from absolute ethanol that had been distilled over NaOH to
remove organic acid) and mixed with 1 5 ml. of dried and distilled
toluene containing the required amount of scintillators, phenylphenyl oxazolc (PPO) and 1 ,Chis 12-( 5-phcnyloxazolyl)] benzine (POPOP). The final composition of the solution was
7 5 % toluene, 2 3 . 7 5 0 / , alcohol and 1.25y0water, each by volume;
t.0 gm./litcr o f PPO and 100.0 mgm./liter of POPOP. T h e
amount of water and alcohol were kept minimal and strictly
constant, since thcy are known to quench the scintillations.
The triplicate samples were counted in a liquid scintillation
counter operating below 0C.and the average value of the three
readings was taken. The reproducibility of the adsorption
procedure and of scintillation counting were checked separately
tiy counting replicate samples and by establishing the linear
relationship between the <:"-activity and counts per minute.
The flotation behavior of quartz as influenced by laurate
and myristate, both in the absence and in the presence of Ca++
ions, was investigated using a modified Halliinond tube technique
as described by Nagy and Van Cleave(*'. Bubble pick-up
tests were also run. Approximately 1.8 gram samples of quartz
were used in the flotation tests. (imditioning prior to flotation
was done by shaking the samples incchanically in polyethylene
bottles from which air had been displaced by nitrogen. Purified
nitrogen was also used in the flotation t a t s .

RESULTS
( a ) Adsorption of Laurate and Myristate:
The adsorption of laurate and myri stare on quartz from
solutions containing (5.0, 12.5 and 25.1) x
gm. ions/liter
of laurate or myristatc respectively, was studied at pH values
ranging from 10 to 12 in the absence of (:a++ or other polyvalent
cations. No adsorption of lauratc or myristate on quartz was
obscrvcd under these conditions.
In spite of the low solubility of calcium soaps, it was possible
to use lauratc ion concentrations up to 2.56 x 1 0 - ~ gni. ions/liter,
in the prescncc of <:a++ ions, without encountering precipitation
of calcium laurate. l\'ith myristate, however, concentrations
as low as 8.X x 10-6 gni. ions/litcr with (:a++ concentrations
as low as 6.99 X 1 0 - 4 gin. ions/litcr, rcsultcd in the formation
of colloidal precipitates of calcium myristate even at a pH
as high as 11.5. No significant results for the adsorption of
myristate ion on quartz in the presence of (:a++ ions could
therefore be obtained.
Preliminary tests with laurate ion in the presence of Ca++
ions indicated that, within the limits of the method used, there
was no detectable adsorption of laurate in the pH range 7.0 to
1 1 .0. .\hove p H 1 1, however, detectable adsorption of laurate
did occur. Hence most of the experimental results to he reported

1965

27

Ca++ conc.'
gm. ions/liter
x 104

Laurate conc.+
gm. ions/liter
x 10'

pH

4.24
6.74
6.74
6.74
11.48
11.48
11.48
14.97

1.01
1.01
1.01
1.01
1.01
1.01
2.56
2.56

11.50
11.31
11.so
1 1.80
11.46
11.52
11.55
11.55

(a)
(b)
(c)
Laurate ads./cm.' No. adsorption No. Ca++ ions No. Laurate ions,
of quartz, g. ions sites/cm.* quartz adsorbed/cm.'
adsorbed/cm.'
x 10"
X lo-"
quartz X lO-I4
quartz X 10-14

2.34
1.83
3.25
1.78
3.14
3.52
9.86
12.79

8.55

3.94

8.55

4.84
-

8.55
8.55
8.55

0.014
0.019
-

7.18
7.18
8.55

0.02 1
0.059
0.077
-

1:0.46:0.002

1:0.57:0.0023
-

1:0.84:0.0025
, 1:0.84:0.007
1:1:0.010

+For 1.81 gram of quartz.

here were obtained from tests done at pH of about 11.5 wherc

the adsorption of Ca++ ions is known to be at a maximum(').
Typical results for the adsorption of laurate on quartz in the
presence of Ca++ ions are shown in Table 1. The number of
adsorption sites/cm.2 of quartz was estimated from the known
specific surface of the quartz sample and the lattice parameters
of quartz. Previous results(1) indicated that a monolayer of

so r

adsorbed Ca++ ions on quartz would be attained at p H 11.5

when the Ca++ concentration in the solution is about 15 x 10-4
gm. ions/liter. Assuming a cross sectional area of 20kz for
laurate ion, the maximum surface coverage (at pH 1 1.5) of
quartz by laurate obtained from a solution containing 1.01 x
gm. ions/liter, is less than 0.5%. With laurate solutions
gm. ions/liter, the maximum surface
containing 2.56 X

90.
80.
70

>

w 60.

50

/
I

g40.

li,/----

2o

lot

L
7

I
8

9
10
INITIAL pH

II

I2

Figure 1 Flotation of quartz with

laurate and myristate in the absence
of Ca++ions.
Flotation time = 5 minutes.
Nitrogen gas flow rate = 45.0 -+ 1.5
c.c./min.
Legend :

0 -1.01

lo-'

gm. ions/liter of
laurate
-2.51 x lod gm. ions/liter of
laurate
0 -12.54 x 10" gm. iondliter of
laurate
I
0 -25.08 x lo-' gm. iondliter of
I
laurate ,
-4.40 x 10d gm. ions/liter of
myristate
-11.0 x lo-' gm. i o d l i t e r of
myristate

0
A

9
10
INITIAL PH

II

12

I'

Figure 2-Flotation
of Ca" activated
quartz with laurate.
Flotation time = 5 minutes.
Nitrogen gas flow rate = 45 2 1.5
e.c./min.
Legend :
0 4 . 2 4 x lo-' gm. ionst'liter of
Ca++ 1.01 x lo-' gm.
I
iondliter of laurate
0 4 . 7 4 x lo-' gm. ionshiter of
1
Cat+
1.01 x 10-6 gm.
ionshiter of laurate
0 -11.48 x 10.' gm. ions/liter of
Cat'
1.01 x lo-' gm.
ions/liter of laurate
A 6 . 7 4 x lo-' gm. ionshiter of
Ca++ 2.56 x 10" gm.
ions/liter of laurate
-11.48 x lo-' gm. ions/liter of
Cat+
2.56 x 10" gm.
i o d l i t e r of laurate

2
3
MINUTES

Figure &Variation of quartz recovery

with time using laurate in the presence
and in the absence of Ca++ions.
Nitrogen gas flow rate = 45 5 1.5
cdions.

pH

= 11.55

Legend :

A-2.56

lo-'

gm. ions/liter of
laurate
0-2.56
x 10" gm. ions/liter of
laurate
11.48 x lo-' gm.
ionshiter of Cat+

-+

The Canadian Journal

of

Chemical Engineering, February, 1965

coverage obtained is between 1 to 2%. The adsorption of

laurate ion on quartz, in the presence of Ca++ ions, is quite
pH dependent and reaches a maximum at pH 1 1 . 5 where the
adsorption of Ca++ ions is also at a maximum.

( b ) Flotation Tests:
Bubble pick-up tests showed no floatability of quartz with
solutions of laurate or myristate at any p H in the absence of
Ca++ ions. This is in agreement with results obtained by other
authors who used a vacuum flotation
However,
slow flotation of quartz from solutions containing (1 .0 and 2.6)
X I O - ~gm. ions/liter of laurate was observed in the Hallimond
tube. Typical results (reproducible within 2-3%) for flotation
tests using laurate and niyristate solutions in the absence of
Ca++ ions are shown in Figure 1 . Quartz recoveries after five
minutes of flotation depend markedly on the collector concentration and pH of the solution. The flotation observed in these
tests appeared to be due to a wcak bubble-particle attachment
and was quite different from that which occurs in the presence
of calcium-activated quartz. In the latter case most of the quartz
collected clung tenaciously to the surface of the solution in
the flotation tube, whereas in the absence of Ca++ ions the
quartz particks dropped from the bubbles before they reached
the solution surface and fell into the collection stem of the cell.
The slow flotation of quartz in the Hallimond tube did not
occur in the absence of collectors and thus is not due to mechanical conveyance. I t is known that the surface tension and
frothing tendency of soap solutions varies in a complicated
manner with composition, p H and timc. The frothing tendency
of soap solutions generally increases with increasing pH and
some weak attachment of quartz particles to soap bubbles
apparently takes place without any sipificant adsorption of the
collector occurring.
The flotation of calcium-activated quartz from solutions
gm. ions of lauratc/litcr
containing (1.01 and 2.56) X
and at p l i values ranging from 7 to 12 was also studied using
the Halliniond tube technique. Results of these tests arc shown
graphically in Figure 2. For solutions containing 1.01 x 10-5
gm. ions/liter of laurate below pH 1 1 .0 the recovery of quartz
was low and the flotation was of the type ohserved in the absence
of Ca++ ions (the flotation under these conditions also tended
to be suppressed by the presence of <:a++ ions due to dccreascd
frothing tendency of the collector). Quartz recovery incrcascd
with increasing pH above 11, reached a inaximuni at pH 1 1.F
and then showed a definite drop at higher pH values. Increasing
the Ca++ ion concentration from 6.74 x lop4to 11.48 x 10-4
gm. ions/liter when the laurate concentration was only 1.01 x
gm. ions/liter, had little or no effect on the extent of quartz
recovery at pH 1 1 . 5 and the flotation rate was still very low.
gm. ions/liter
With a laurate concentration of 2.56 X
the effect of increasing the Ca++ ion concentration was more
noticeable; quartz recoveries were of the order of 90% in 5
minutes and flotation rates were noticeably greater. Above
pH 1 1.5 no drop in quartz recovery or flotation rate was observed
gm.
when the laurate concentration was at least 2.56 x
ions/liter and the Ca++ concentration was 11.48 X 10-4 gm.
ions/litcr, in contrast to the behavior shown for lower <:a++
and lauratc ion concentrations.
The variation of quartz recovery with time when laurate
solutions of 2.56 X
gm. ions/litcr were used in the presence
of 11.48 x 1 0 - ~ gm. ions of Ca++/liter and with no (:a++ ions
present, is shown in Figure 3. The flotation rare was 3 to 4
times as great in the presence of <:a++ ions as in its absence and,
as noted above, the flotation appeared to be of an entirely
different type in the two eases.
Bubble pick-up tests showed definite floatability of quartz
with laurate in the presence of Ca++ ions in the pH range
where flotation was found to be appreciable in rhe Halliniond
tube tests.

DISCUSSION
The flotation of quartz by soap solutions in the presence of
polyvalent cations has been investigated by several workers
and the subject has been briefly reviewed in Part I of this work").
By measuring the C"-activity on solid quartz, Gaudin and
<:hang(x) found considerable abstraction of laurate even on the
unactivated quartz @a++ absent). Their vacuiini flotation
technique did not indicate any flotation even though the amount
of laurate so abstracted seemed to approach a monolayer. Some
uncertainty exists as to whether these authors were measuring
adsorption of lauratc or nicrely abstraction of it by the solution
adhering to the solid. h later study by Gaudin and Fuerstenau(4)
showed that the zeta-potential of unactivated quartz was not
affected by the addition of laurate, thus indicating no adsorption
of laurate on quartz under these conditions.
The results of the present \vork indicate that within the
detectable limits, laurate and rnjrristatc ions are not adsorbed
on quartz in the absence of a polyvalent cationic activator such
as (:a++, nor do thc soap solutions promote a rapid flotation
of quartz under these conditions. .llso, no adsorption of laurate
on quartz was detected bclow pH 1 1 in the presence of Ca++
ions (at the concentrations used in the present work) and quartz
shows little tendency to float under these conditions. The
extent of surface coverage of quartz by (:a++ under these eondirions has been found to be Icss than 5 O o j o ~ and
~ ) the distribution
coefficient of lauratc ion between the quartz surfacc and solution
seems to be considerably less than unity.
Under conditions where the adsorption of (:a++ ions on
quartz is a maximum (pH 1 1. F), the adsorption of laurate although
measurable, is quite small in comparison to that of Ca++ ions as
indicated by the ratio a:b:c in Table 1 . The low solubility of
the calcium salt of lauric acid severely limited the concentration
range over \vhieh the study could be made. IVith the highest
concentration of laurate employed, the maximum extent to
which the calciuni-acti\.atcd quartz surface was covered with
laurate was between 1 and 2%. The flotation tests indicated
that although a mininiuni amount o f lauratc ion must be present
for effectivc flotation of calcium-activated quartz to occur at
pH 1 I . 5 , only 1 to 2% of the surface needs to be covered with
adsorbed laurate.
In general, flotation of calcirim-acti\,ated quartz with laurate
is minimal at pH 7, increases with increasing pH, Ca++ and
laurate ion concentrations and reaches a maximum valuc at
pH 1 1 . 5 . At relatively low (:a++ and laurate ion concentrations,
a definite decrease in the floatability of quartz was observed
at a pH just above 1 1 . 5 . This corresponds to the observed
decrease in the adsorption of Ca++ ions on quartz under similar
conditions('). Within the solubility limits of calcium laurate
the decrease in quartz floatability above pH 1 1 . 5 was not
observed when the <:ai ion concentration was greater than
1 1.48 X 1 0 - 4 gm. ions/litcr and the laurate concentration was
2.56 X
gm. ions/liter. The deercased floatability of quartz
above p l l 1 1 . 5 is thus only apparent when the laurate coneentration is bclow a limit which occurs between (1.0 and 2.6)
X lop5gm. ions/litcr. This effect may be partly due to the
depressor action of silicate ions formed by the action of NaOH
on quartz.
+

Acknowledgements
Financial assistance provided by the National Research Council of
C;innd;i throuxh a grant-in-aid of this research is pratcfnlly acknowledged.
B. M . Craig of the Prairie Regional Liihoratory of the National Research
Conncil kindly did thc chrom;itographic analyses of the fatty acid
sumplr. S . hl. Ahnied expresses hls apprcciation to The Consolidated
Mining and SmtWng Company of Canadit for the Cominco Fellowship
awarded to him.

The Canadian Journal of Chemical Engineering, Februury, 1965

References
( 1 ) Ahmid. S. hl. and \'an Cleave, A. B., Can. J. Chem. Eng. 43, 23
i 1 afin .
( 2 ) N%Y,, E . and Van Cleave, A. B.. Can. J. Chem. Eng. 40, 76 (1962).
( 3 ) Gaudin. A. hl. and Chang, C. S., Trans. A.I.M.E. 193, 193 (1952).
( 4 ) Gaudin. A. hl. and Flierstenan, D. W., Trims. A.I.M.E. 202, 66

I VW.,,

(1955).

* * *
29