389

Canadian Metallurgical Quarterly, Vol 49, No 4 pp 389-396, 2010

Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

Frother Analysis in Industrial Flotation Cells

A. Zangooi, C.O. Gomez and J.A. Finch
Department of Mining and Materials Engineering, McGill University
Montreal, QC H3A 2B2, Canada
jim.finch@mcgill.ca

(Received in revised form August, 2010)

Abstract Flotation is a separation process based on the collection of particles on the surface of
bubbles. Flotation machines disperse air into bubbles using a variety of techniques. The characteristics of
the bubble population are strongly affected by the selection of frother type and concentration. As
metallurgical results depend on the properties of the bubble swarm, the measurement of frother
concentration is vital to understand and control performance. A previously developed colorimetric
technique was refined to increase analysis rate and reproducibility, particularly for low-solubility frothers.
The refinements include new procedures for preparation of standards and samples, for constructing
calibration curves and for establishing the reproducibility and accuracy of the technique. The refined
technique has been demonstrated to be robust, reliable and accurate. The refinements are briefly discussed
and documented. This paper focuses on applications of the technique in operations such as determination
of frother remnant levels in recycle water, reliability of frother delivery and frother dissolution and in
support of research interests related to gas dispersion and characterization of frother partitioning.
Rsum La flottation est un procd de sparation bas sur la collecte de particules la surface des bulles.
Les appareils de flottation dispersent de lair sous forme de bulles au moyen de techniques varies. Les
caractristiques de la population de bulles sont fortement affectes par la slection du type de moussant et sa
concentration. Comme les rsultats mtallurgiques dpendent des proprits de lessaim de bulles, la mesure
de la concentration du moussant est vitale la comprhension et au contrle du rendement. On a raffin une
technique colorimtrique, dveloppe auparavant, pour augmenter la vitesse danalyse et la reproductibilit,
particulirement pour les moussants faible solubilit. Les raffinements incluent de nouvelles procdures
pour prparer les talons et les chantillons, pour construire les courbes de calibration et pour tablir la
reproductibilit et la prcision de la technique. On a dmontr que la technique raffine tait robuste, fiable
et prcise. On discute brivement des raffinements et on les documente. Cet article se concentre sur les
applications de la technique dans les oprations comme les niveaux du reste de moussant dans leau de
recyclage, la fiabilit de la livraison du moussant et de sa dissolution et sur le soutien des intrts de recherche
relis la dispersion de gaz et la caractrisation du partitionnement du moussant.
Keywords: Colorimetry, Frothers, Flotation, Frother analysis, Frother partitioning

INTRODUCTION
Measurement of gas dispersion parameters (gas velocity, gas
holdup and bubble size) has become a tool to characterize
industrial flotation cells, for example, establishing the
operating range and the relationship to metallurgical
performance [1,2]. Gas dispersion properties are affected by
frother concentration. Calculating frother concentration
from dosage in an operating plant is difficult due to factors
such as incomplete dissolution and unknown distribution
between pulp and froth. Several commercial frothers are

blends and it is the relative proportion of each that affects

gas dispersion. Other complications are alcohol contaminants in some other reagents (e.g. xanthates) and residual
frother in recycle waters. There is, therefore, need of an
analytical technique.
A colorimetric technique for measuring frother concentration in samples of plant streams was introduced by Glinas
and Finch [3]. A review of experiences showed the potential
for process diagnoses and optimization [4]. The analysis
results demonstrated, for example, the effect of location and
dosages at frother addition points and the presence and
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A. Zangooi, C.O. Gomez and J.A. Finch

390

concentration level of remnant frother in recycle and

process waters. Frother mass balances around circuits were
closed with minor differences.
The original technique, however, had a fairly low
analysis rate (4 to 6 per day) and limitations when applied to
low solubility frothers. Refinements were sought to make
the technique suitable to the wide range of frothers and to
speed up analysis while retaining reliability. A major need
was to integrate frother analysis with gas dispersion characterization measurements to help establish whether
inconsistent results were a consequence of changing frother
concentrations. In addition to providing frother concentration for interpreting gas dispersion measurements, it is
anticipated that the frother analysis procedure can be used to
establish potentially important operational details, for
example, how thoroughly a frother dissolves, how reliable
and stable frother delivery is, how evenly frother is
distributed down a bank and between lines and how frother
distributes between pulp and froth (partitioning).
The purpose of this paper is to briefly describe the
refinements to the analysis technique and then to
demonstrate the potential for identifying plant operational
issues related to frother.
FROTHER ANALYSIS TECHNIQUE
The colorimetric frother analysis is based on the
Komarowsky reaction for the analysis of aliphatic alcohols
[5] and was first used for a frother, MIBC (methyl-iso-butylcarbinol), by Parkhomovski et al. [6]. The Komarowsky
reaction involves the interaction of a frother (specifically
the OH group), concentrated sulphuric acid and an
appropriate aldehyde. The color formation is due to a
dehydration of the frother by the sulphuric acid and the
reaction of the unsaturated hydrocarbon with the aldehyde.

Sample Chloroform

A calibration curve of concentration vs. absorbance (at a

selected wavelength) is constructed.
The analysis involves four stages, illustrated in
Figure 1:
Extraction of frother from the sample into chloroform
(done twice), which is accomplished by shaking the
sample and 10 mL of chloroform in a separatory
funnel. The denser chloroform (20 mL) is collected in
a 70 mL glass vial and the aqueous phase discarded.
Extraction of frother from the chloroform into
sulphuric acid, which is done by shaking the
chloroform and 10 mL of highly concentrated
sulphuric acid in a separatory funnel. The denser acid
is collected in a 70 mL glass vial and the chloroform
discarded.
Execution of Komarowsky reaction to produce
coloured products by adding 0.1 mL of the colour
indicator (aldehyde dissolved in acetic acid) to the vial
containing the sulphuric acid. The mixture is
maintained in boiling water for 15 minutes and then
immersed in an ice bath to stop the reaction.
Collection of UV absorbance spectrum of the coloured
solution using a quartz cell.
There are two types of samples to be prepared:
standard solutions to construct the calibration curve and
samples for analysis. The standards are prepared by taking
volumes of a stock solution into a 100 mL volumetric flask
containing 15 g of sodium chloride and then filling up to
volume with water. The sodium chloride facilitates
migration of frother molecules from the aqueous phase to
the chloroform and reduces the formation of foam. In the
case of analysis, the 100 mL volumetric flask (with the
sodium chloride) is filled up to volume with water filtered
from the pulp sample. Dilution with water may be necessary
for samples with concentrations above the calibration curve
range.

Dehydration reactions:
H2SO4
H+ + HSO4

Sulfuric acid
Chloroform

RCHOH + H+

RCH+ + H2O

Discarded chloroform
Discarded water
Sulfuric acid + Colour indicator

Boiling water
(15 min)

Ice bath

UV absorbance measurement
Fig. 1. A schematic of the procedure for colorimetric analysis of frothers.

Canadian MetallurgiCal Quarterly, Vol 49, no 4

Frother Analysis in Industrial Flotation Cells

Wavelength, A
Fig. 2. Effect of water source on absorbance spectra of 10 ppm standard.

ANALYSIS REFINEMENTS
The application of the frother analysis technique in plant
demonstrated that improvements were required. Some
variability between operators was noted and reproducibility
was poor for low solubility frothers. A systematic tracking of
error sources produced new procedures in two areas,
preparation of samples and standards and construction of
calibration curves that significantly improved reliability.
Preparation of Samples and Standards
Stock Solution: The preparation of frother solutions with
concentrations in the ppm range involves the precise
weighing of a few mg of a viscous liquid. The original
procedure called for a stock solution, 1 L at 500 ppm, to be
used to prepare the standards by dilution. The preparation of
stock solution was changed from volume-based to massbased and to a larger and more dilute solution (2L, 25 ppm).
The lower concentration facilitated complete dissolution in
the case of low solubility frothers. The preparation considers
weighing drop by drop to have close to but less than the 50
mg of frother required and then adding the weight of water
calculated for a 25 ppm solution.
Choice of Water: Analysis of plant samples presents a
challenge in deciding what water to use in the preparations of
standards as water quality affects the colour (and absorbance).
In plants there are normally two sources of water: tap (potable)
and process waters. The first step in the analysis, extraction of
the frother into an organic layer of chloroform was expected to
be independent of inorganic contaminants. Experience
demonstrated, however, that components other than frother in
the process water are also apparently extracted and affect the
absorbance of the final solution. This is illustrated in Figure 2,
which compares UV absorbance spectra for a 10 ppm solution
of a frother prepared using tap and process waters.
Process water seems the better option but this water
often contains varying levels of remnant frother. The frother
residual concentration can be estimated by comparing

Other Organics: Any OH-containing organic is a likely

interferent. One known example derives from collectors which
are sometimes diluted with organic solvents to reduce viscosity
and facilitate delivery. These solvents are usually low
molecular-weight alcohols that, for the purpose of analysis,
have a response similar to frothers. The construction of a
calibration curve for the collector in use is then recommended
to establish how significant the contribution is. Most
experience to date indicates that the effect of collector on
absorbance is significantly smaller than that of frother (Figure
4). For the example in Figure 4, if not accounted for, 10 ppm of
collector will increase the estimated frother concentration by
about 2 ppm. Separation of the contributions of two or more
organic components is currently being pursued.

Frother concentration, ppm

Absorbance

Process water

calibration curves constructed using tap and process waters

(Figure 3). The process water curve showed the same slope as
the tap water, with the higher absorbance in process water
interpreted as due to remnant frother, in this case between 14
and 15 ppm. It is recognized, however, that the higher
absorbance may be the consequence of more than one
compound participating in the Komarowsky reaction.

Tap water
Process water

Absorbance
Fig. 3. Calibration curves obtained in tap and process water

Concentration, ppm

Tap water

391

y = 93.2x + 0.4

y = 22.5x + 0.0

Frother

Collector

Absorbance
Fig. 4. Calibration curves in tap water for the combination frother/collector
in use at a concentrator.

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392

The construction requires selection of a wavelength for

extracting absorbance from the spectra. The original procedure
recommended the use of the wavelength with the maximum
absorbance to obtain a curve with a minimum slope (i.e., largest
absorbance difference for a given concentration difference),
which should result in a most accurate measurement.
This did not always prove to be the case, sometimes
there was more scatter around the calibration line for the
absorbance at maximum wavelength. A different criterion to
select the wavelength was developed based on minimizing
the sum of squares of residuals (the difference between true
and estimated frother concentration using the calibration
curve), SSR. The difference between the two approaches is
illustrated in Figure 5 for the frother F-150 (a polyglycol
supplied by Flottec Inc.). The maximum absorbance occurs at
a wavelength of 474 A and the corresponding SSR for the
calibration line is 0.711 ppm2. The minimum SSR
corresponds to a wavelength of 528 A (SSR 0.259 ppm2).
The respective errors (95% confidence interval) for a sample
reporting a concentration of 5 ppm (middle of the calibration
curve range) are 1.27and 0.77 ppm for the calibration at
wavelengths 474 and 528 A.
Statistical considerations are also used to select concentrations for the standards, which must be chosen to have an
average at around the value expected in the plant samples or
that aimed at by sample dilution. Concentrations at the middle
of the calibration curve range have the least error.
REPRODUCIBILITY
The use of the refined technique significantly improved
reproducibility. Exercises to quantify reproducibility which
can be considered as an additional refinement are routinely
performed given the diverse conditions found in the field.
The procedure involves running five analyses in each case.
Every day, a 25 ppm stock solution is made and five 5 ppm
samples are prepared and analyzed. Typical results are
summarized in Table I that includes, in this case, absorbance
for 5 ppm frother solutions prepared from the same and
from different stock solutions.
These results demonstrate high reproducibility (narrow
absorbance ranges around the average) in the preparation of

Frother concentration, ppm

Construction of Calibration Curves

y = 14.04x + 0.32

y = 9.16x + 0.53

474 A
528 A

Absorbance
Fig. 5. Calibration curves obtained at different wavelength.

samples and standards. As expected, the reproducibility for

samples prepared from the same stock solution (columns in
Table I) is smaller than that obtained when preparation of
the stock solution is included (rows in Table I).
Such results which are collected in the laboratory prior
to industrial testing establish a baseline for the expected
reproducibility at the plant. Our experience is that although
the average absorbance may be different between lab and
plant, because of different water qualities, standard
deviations remains similar when the same operator,
equipment and reagents are used (normally the case). When
standard deviations have been higher at the plant, attempts
are made to identify the source of additional error. These can
range from water quality issues to frother properties that
make necessary special precautions for storing stock
samples.
INDUSTRIAL APPLICATIONS
Characterization of Gas Dispersion
One of the needs for frother analysis is to support gas
dispersion characterization in industrial units. In some cases,
gas dispersion results prove quite variable in spite of
operation under nominally the same conditions. One cause of
variation might be frother concentration, perhaps as a

Table 1 Results of reliability determination tests

Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Average
95% C.I. range

Stock 1

Stock 2

Stock 3

Stock 4

Stock 5

Average

95% C.I. range

1.561
1.539
1.546
1.531
1.562
1.548
0.019

1.609
1.645
1.626
1.611
1.641
1.626
0.024

1.600
1.644
1.611
1.627
1.601
1.617
0.027

1.613
1.625
1.632
1.617
1.609
1.619
0.013

1.589
1.610
1.596
1.580
1.621
1.599
0.023

1.594
1.613
1.602
1.593
1.607
-

0.030
0.062
0.049
0.055
0.042
-

Canadian MetallurgiCal Quarterly, Vol 49, no 4

Frother Delivery

Gas Holdup, %

To test consistency in delivery, pulp samples from one cell

were collected over time (11:45 to 14:15) with frother dosage
nominally steady. Later the tonnage was reduced to one half the
original (17:00) and additional samples were collected (19:00

Day 1

Day 2

Gas Velocity (cm/s)

Fig. 6. Cell characterization curves: illustration of reproducibility.

393

Day 1
Day 2
Day 3
Day 4

Gas Velocity (cm/s)

Fig. 7. Example of inconsistent gas dispersion results.

to 19:55). The results showed small frother variations from 13

to about 15 ppm (Figure 8).
As frother is metered based on solids tonnage (i.e.,
g/tonne) and not with the purpose of achieving a certain liquid
phase concentration in the cell, variations such as in Figure 8
may be expected. Whether these variations impact
metallurgical performance as a consequence of changes in
bubble size (concentrations in this case are close to the usual
CCC range) and froth characteristics may determine the level
of effort warranted to correct it. The frother delivery system did
handle the 50% tonnage reduction well, (pulp density was
maintained) keeping the concentration close to the same range.
Measurement of frother concentration down a bank is
another way to assess frother delivery. The example in Figure
9 shows the bank concentration profile has a pattern,
decreasing from about 28 ppm at the head of the bank (cell 1)
down to ca. 22 ppm at mid-bank then rising again, that may
reflect a cyclical variation in the feed concentration associated
with the delivery system. These results do suggest that frother
concentration are higher than necessary for controlling bubble
size, a consequence, in this case, of a high frother content in the
recycle water. The concentration in the feed to the bank is
higher than that measured in any cell and may reflect

Frother Concentration (ppm)

consequence of issues created by delivery of a small flow of a

relatively viscous liquid.
Two applications of gas dispersion are: diagnosis of a
cells ability to disperse air [7] and optimization of
metallurgical performance through determination and control
of bubble surface area flux [8,9,10]. In the case of cell
diagnosis, gas dispersion measurements may be reported as gas
hold-up vs. gas velocity plot (referred as a cell characterization curve). Cell characterization curves show, in general,
good reproducibility as illustrated in Figure 6 for
measurements in the same cell on two different days. Curves
have similar slopes and show systematic gas hold-up
differences (of about 1% in this case) for the same gas velocity,
which is not considered significant.
The effect of frother concentration fluctuations may be
more significant on bubble size than on gas hold-up, depending
on the concentration relative to the CCC (critical coalescence
concentration [11]). Bubble size is used in generating plots of
bubble surface area flux vs. gas velocity. In this case, we often
find less consistency, as evidenced in Figure 7 and variations in
frother concentration may be the explanation. In the case
illustrated, Day 1 showed poor reproducibility around a gas
velocity of 1 cm/s (the normal operating value). The results
from Day 2 gave the same trend with gas velocity (similar
slope), but with values 40% smaller. The results for Day 3
showed, if anything, a decreasing trend, while the results for
Day 4 showed increasing values of flux for the same gas
velocity. It is crucial to establish the source of these variations
to define corrective actions leading to steadier operation,
presumably the desirable outcome. Variation in frother concentration was the prime suspect but at the time there was no
method to determine it. Evidence was sought subsequently by
examining constancy of frother delivery.

Bubble Surface Area Flux (l/s)

Frother Analysis in Industrial Flotation Cells

Time
Fig. 8: Frother concentration measured in a cell over time.
Canadian MetallurgiCal Quarterly, Vol 49, no 4

A. Zangooi, C.O. Gomez and J.A. Finch

394

Frother Concentration (ppm)

Tail samples

Concentration, ppm

Concentrate samples

Circuit

Cell
Fig. 9. Frother concentration profile measured in a nine-cell bank.

Fig. 11. Frother partitioning in cells down a bank (rougher).

partitioning of frother to the froth, another factor that can now

be explored.
The range of frother concentration variations measured in
and between cells prompted the determination of errors to
establish whether the measured differences were statistically
significant. The refinements associated with the construction of
calibration curves are a consequence of this need and errors
have been consistently reduced (for example from 2.3 ppm at
95% confidence level (Figure 8) to 1.4 ppm for the results
presented in Figure 9, to currently less than 1 ppm).

ppm.) Partitioning must induce several consequences: among

them moderating gas dispersion (by reducing frother concentration in the pulp) and froth properties; influencing
subsequent cell behaviour; and influencing downstream
circuit performance.

Frother Distribution between Pulp and Froth Zones

(Partitioning)
Frother adsorbs on the bubble surface and thus transfers
(partitions) to the froth and releases to the water as bubbles
burst. This is expected to increase frother concentration in the
overflowing (concentrate) water. This phenomenon has been
demonstrated in the laboratory [12] and the plant [4].
Frother partitioning is evident in circuit streams (Figure
10) and potentially more interesting in individual cells in a
bank (Figure 11). (Analytical error in these cases is 0.5

CONCLUSIONS
The colorimetric technique for frother analysis in industrial
streams was refined to increase analysis rate and
reproducibility, particularly for low solubility frothers. The
refinements include procedures for preparation of standards
and samples and constructing calibration curves. The refined
technique proved to be reproducible and accurate in both
laboratory and plant environments.
Examples from plant experiences illustrate uses in
tracking variations in frother feed between cells and circuits
and partitioning between pulp and froth. The technique is
becoming integrated into flotation characterization and
diagnostic work.
ACKNOWLEDGEMENTS

Tail samples

Funding of this work is through the Chair in Mineral

Processing co-sponsored by Vale Inco, Teck Cominco, Xstrata
Process Support, Agnico-Eagle, Shell Canada, Barrick Gold,
SGS Lakefield Research, COREM and Flottec under the CRD
(Collaborative Research and Development Program) of Natural
Sciences and Engineering Research Council of Canada
(NSERC) and through the AMIRA P9O project also under an
NSERC-CRD.

Concentration, ppm

Concentrate samples

Roughers

Cleaners

REFERENCES

Cleaner Scavengers

Circuit
Fig. 10. Frother partitioning in different circuits.

Canadian MetallurgiCal Quarterly, Vol 49, no 4

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