Effects of Frother Type on Single

Bubble Rise Velocity

Amir Arash Rafiei Mehrabadi

Department of Mining, Metals and Materials Engineering

McGill University
Montreal, Canada

June 2009

A thesis submitted to McGill University in partial fulfillment of

the requirements for the degree of Master of Engineering

© Amir Arash Rafiei Mehrabadi, 2009

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Abstract

The addition of frother in flotation has two main functions, to help reduce bubble
size and help produce a stable froth. A role of frother on bubble behavior in pulp
zone is usually not considered. A previous study showed that as frother type was
changed the same gas holdup was given by different size bubbles. This implies
that bubble rise velocity depends on the nature of the surfactant (frother type). A
study using bubble swarms appears to support the frother type effect but bubble
interactions are a possible confounding factor.

This study resolved the question by measuring terminal rise velocity profile of
single bubbles (ca. 1 to 2 mm) as a function of frother type. It is shown that at the
concentrations of interest in flotation, 1-pentanol hardly alters the velocity
compared to water alone while F150 (a polyglycol) reduces the velocity by up to
50%. The results become in 1-pentanol bubble did not reach terminal velocity.
For high concentration of 1-pentanol (>130ppm) the rise velocity is reduced
comparable to F150.

To investigate, experiments were performed using aliphatic alcohols from 1-

butanol (C4) to 1-octanol (C8). It was found there is a minimum concentration for
the frother to give terminal velocity close to the Clift et al. contaminated eater
result. The concentration decreases as molecular weight (chain length) of alcohol
increases. Larger bubbles (1.8 vs. 1.5mm) require higher minimum
concentration.

To study the influence of molecular structure, three 6-C alcohols, 1-hexanol,

MIBC and 2-hexanol, were used. The results show that molecular structure
influences rise velocity through the position of OH group, and whether the alcohol
is straight chained or branched. The observation can make a useful link frother to
chemistry for understanding frother influence on bubble rise and possibly its
function in flotation.

The influence of three industrial frother, MIBC, F150 and DF250, was studied
and it was observed that over the practical concentration range all reduce rise
velocity similar to contaminated water and their critical concentration are very low
compared to the aliphatic alcohols. In addition, the influence of a salt, NaCl, on
bubble rise velocity was compared to MIBC and confirms a previous observation
that reported the similar capability of NaCl to act like MIBC.

ii
Résumé

Deux raisons principales commandent à l´ajout de la mousse dans le processus

de flottation, à savoir, la réduction de la bulle et la production d´une mousse
stable. L´effet de la mousse sur le comportement de la bulle en zone pulpaire
n´est pas pris en compte. Un travail antérieur a démontré que pour la même
fraction d´air transporté par les bulles, le type de mousse a de l´influence sur la
taille des bulles. Cela implique que la vélocité de la bulle dépend de la nature du
surfactant (type de mousse). Une étude basée sur l´usage de plusieurs bulles
semble s´accorder avec l´hypothèse relative au type de mousse, néanmoins les
interactions des bulles rendent le problème complexe.

La présente étude a résolu cette question en mesurant la vélocité d´une bulle

dont les dimensions sont presque égales à 1 ou 2 mm, suivant le type de
mousse. Il en est résulté que dans l´intervalle des concentrations d´importance
en flottation, le pentanol peine à influencer la vélocité, alors que l´eau toute seule
en serait capable. En revanche, le F150 (un polyglycol) réduit la vélocité de 50%.
Pour les concentrations élevées de pentanol (>100 ppm), la vélocité décroit et
devient comparable à celle engendrée par la présence du F150. Il va de soi que
l´observation antérieure est confirmée dans l´intervalle pratique des
concentrations.

En guise d´investigations, des expériences au cours desquelles les alcools

aliphatiques allant du butanol (C4) à l´octanol (C8), ont été réalisées. Il a été
démontré que l´effet du type de mousse sur la vélocité dépend de la
concentration. Il existe une concentration minimale de la mousse en dessous de
laquelle, la bulle monte comme dans le modèle de l´eau contaminée de Clift et
al. La concentration minimale critique dépend de la dimension de la bulle et du
déplacement mesuré à partir du point terminal du tube capillaire. L´on rapporte
que les bulles les plus larges et les mousses de petite masse moléculaire
nécessitent une concentration élevée pour épouser le comportement de l´eau
contaminée. Au dessus de cette concentration, la vélocité de la bulle est
indépendante du type de mousse et de la concentration.

Afin d´étudier la possible influence de la structure moléculaire, trois alcools (C6)

dont 1-hexanol, MIBC et 2-hexanol ont été utilisés. Les résultats ont montré que
la structure moléculaire influence la vélocité via la position du groupe OH, selon
qu´elle est linéaire ou ramifiée. Cette observation fait clairement un lien avec la
chimie et permet de mieux comprendre la relation entre la mousse et la vélocité
de la bulle et possiblement sa fonction. L´influence de 3 mousses
industrielles dont le MIBC, le F150 et le DF250, a été étudiée. L´on a observé
qu´au - delà de l´intervalle pratique de concentrations, ces mousses réduisent la
vélocité de la même manière que l´eau contaminée. Leurs concentrations
critiques sont de beaucoup inferieures à celles des alcools aliphatiques. En plus,
l´influence du sel (NaCl) sur la vélocité a été comparée à celle du MIBC. Cette
expérience a confirmé que le NaCl peut se comporter comme le MIBC.

iii
Acknowledgements

I wish to express my sincerest appreciation and utmost gratitude to my

supervisor, Professor James A. Finch, for his guidance, support, patience,
continuous encouragement, trust, discussions, valuable technical assistance,
very high teaching skills and especially his brilliant vision about the current
research. During all precious days of my work at McGill his integrity, discipline,
well-organized planning, timing and attitude gave me very important experiences
and ideas to be more successful in my future life. Briefly, as a very important key
of success that I have learned, he is one of the people who really enjoys from his
work life.

I would like to thank Dr. Ram Rao who helped me to understand some problems
in organic chemistry. Also I want to thank Dr Cesar O. Gomez for all his efforts in
preparing the column for running experiments and his brilliant engineering ideas
in re-designing the column for providing better performance.

Thanks must go to my colleagues for providing support and very good

collaboration, especially Dr. Mitra Mirnezami for her advice and help.
I would like to gratitude the organizations and companies that provided sufficient
financial support for doing my work.

The last but the most gratitude must go to my family and especially my mother
who means every thing to me.

iv
Table of Contents
1. INTRODUCTION 1
1.1. Single bubble rise velocity 1
1.2. Velocity profile and terminal velocity of a single bubble 2
1.3. Objectives of the study 4
1.4. Structure of the thesis 5
2. BACKGROUND 6
2.1. Bubble formation in gas-liquid systems 6
2.2. Theoretical aspects 6
2.2.1. Forces 6
[Link]. Surface tension 7
[Link]. Buoyancy 7
[Link]. Drag 8
2.2.2. Force ratio 8
2.2.3. Wake phenomenon 10
2.3. Surfactants and their influence at air/water interface 11
2.3.1. Surfactant and frother 11
2.3.2. Surfactant adsorption mechanism 12
2.3.3. Surfactant distribution 13
2.3.4. Some consequences of presence of surfactant at air/water
15
interface
[Link]. Marangoni effect 15
[Link]. Interaction between surfactant and water molecules 17
[Link]. Effect on bubble internal circulation 17
2.4. Bubble behavior 18
2.4.1. Bubble size 20
2.4.2. Bubble shape 21
2.4.3. Bubble rise path 24
2.4.4. Bubble rise velocity 25
[Link]. Factors affecting the rise velocity 26
2.4.5. Formulation for rise velocity correlation 30
2.5. Contaminants and rise velocity 30
2.5.1. Surfactant 30
[Link]. Newtonian liquids 30
[Link]. Non-Newtonian liquids 32
[Link]. High viscosity liquids 32
[Link]. Simulation and numerical analysis 32
2.5.2. Frothers 33
2.5.3. Salts 36
3. EXPERIMENTAL SETUP 39
3.1. Equipment 39
3.1.1. Column setup 39
3.1.2. Air line 39
3.1.3. Camera moving device 39
3.1.4. Capillaries 41
3.2. Requirements 41

v
 3.2.1. Temperature control 41
3.2.2. Bubbling frequency 41
3.2.3. Water saturation 41
3.3. Procedures 41
3.3.1. Bubble velocity profile 41
3.3.2. Data Processing 42
3.4. Reagents 43
3.5. Measurement techniques 45
3.5.1. Bubble position 45
3.5.2. Local velocity 45
3.5.3. Bubble size 46
3.5.4. Reagents and choice of reagent concentration 47
[Link] AND DISCUSSION 49
4.1. Reliability 49
4.1.1. Bubble generation 49
4.1.2. Terminal velocity 51
4.1.3. Bubble size 53
4.2. Velocity profile analysis 54
4.2.1. Examples 54
4.2.2. Maximum velocity 56
4.3. Reagent type: pentanol vs. F150 57
4.3.1. Velocity profile 57
4.3.2. Comparison of terminal/apparent terminal velocities 58
4.4. Aliphatic alcohols 59
4.4.1. Concentration effect 62
4.4.2. The influence of molecular structure: C-6 alcohols 69
4.4. Comparison of MIBC and NaCl 72
4.6. Comparison of frothers 74
4.7. The dependency of terminal velocity on frother properties 76
5. CONCLUSIONS AND RECOMMENDATIONS 80
5.1. Conclusions 80
5.1.1. Bubble generation 80
5.1.2. Velocity profile analysis 80
5.1.3. Hypothesis based on observation of Azgomi et al. (2007) 80
5.1.4. Aliphatic alcohols 81
5.1.5. The comparison of MIBC and NaCl 81
5.1.6. Commercial frothers 82
5.1.7. Dependency of terminal velocity on frother properties 82
5.2. Recommendations for future works 82
Refferences 84
Appendix 99

vi
List of Figures
Figure 1.1: The stages of a typical velocity profile 3
Figure 1.2: Typical trend for terminal rise velocity in clean and 4
contaminated water
Figure 2.1: Circulation region (wake) behind a sphere at various Reynolds 11
numbers
Figure 2.2: Accumulation of surfactant at air/water interface 14
Figure 2.3: Surfactant and velocity distribution on bubble surface for the 15
two extremes
Figure 2.4: The distribution of adsorbed surface active solute on the 16
surface of a rising bubble
Figure 2.5: The internal circulation of moving fluid showing the direction of 18
relative flow: (a) complete circulation, (b) part circulation, (c) stagnant
Figure 2.6: The relationships between identified factors that affect bubble 20
behavior
Figure 2.7: Illustration of dynamic pressure causing bubble deformation in 22
water only case (a), and the force created by surface tension gradient that
occurs in presence of surfactant that resists deformation (b) (Finch et al.,
2008).
Figure 2.8: Bubble shape regime 23
Figure 2.9: Typical trends in rise velocity with bubble size for pure and 27
contaminated liquids
Figure 2.10: Effect of initial bubble deformation on terminal velocity in 27
distilled water
Figure 2.11: a. Velocity profiles for 2.2mm bubbles in MIBC, b. Terminal 34
velocity vs. bubble size in the presence of some frothers
Figure 2.12: Bubble size measurement at same gas holdup (8%) for F150 35
and Pentanol
Figure 2.13: Comparison between influences of F150 and Pentanol on 36
terminal rise velocity of bubbles in swarms
Figure 2.14: Suggested explanation for action of high concentration salts 37
which act like frother
Figure 2.15: Influence of potassium chloride concentration on terminal rise 37
velocity
Figure 3.1: The experimental column setup 40
Figure 3.2: The data processing flowchart 43
Figure 3.3: The required information for measuring bubble height during 45
rise on one image
Figure 3.4: The applied technique for measuring local velocity 46
Figure 3.5: The technique applied for measuring bubble size 47
Figure 3.6: The description of technique that applied to determine 47
equivalent concentrations of F150 and 1-Pentanol
Figure 4.1: Variation of single bubble size vs. bubble frequency for 50
reagents using 25μm capillary.
Figure 4.2: The variation of single bubble size vs. bubble frequency for the 50
three applied capillaries

vii
Figure 4.3: Bubble size as a function of equivalent concentration for 25μm 51
capillary
Figure 4.4: An example of velocity profile where bubble reaches terminal 52
velocity in F150 1ppm for ca. 1.45mm bubble
Figure 4.5: An example of measuring terminal rise velocity and reliability 53
Figure 4.6: Velocity profiles in F150 55
Figure 4.7: Velocity profiles in F150 (ca 1.5mm) over the first 3 seconds for 55
conditions in Figure 4.6.
Figure 4.8: The influence of reagent concentration on maximum velocity in 56
the presence of MIBC, NaCl and F150
Figure 4.9: Velocity profiles in F150, 1-pentanol and tap water 58
Figure 4.10: The terminal/apparent terminal rise velocity vs. bubble 59
diameter at 500 and 3000mm distance in the presence of F150 and 1-
Pentanol compared to swarms results (Acuna and Finch, 2008) and results
for single bubble in clean and contaminated water given by Clift et al.
(1978)
Figure 4.11: The terminal/apparent terminal rise velocity vs. bubble 60
diameter at 3000mm in the presence of low (1) and high (5) concentrations
of 1-pentanol, 1-hexanol and 1-heptanol
Figure 4.12: The terminal/apparent terminal rise velocity vs. bubble 61
diameter at 3000mm in the presence of low (1) and high (5) concentrations
of 1-butanol, 1-hexanol and 1-octanol.
Figure 4.13: Velocity profiles in 1-hexanol (ca 1.5mm) 61
Figure 4.14: Velocity profiles in 1-butanol (ca 1.45mm) 62
Figure 4.15: Velocity profiles in 1-pentanol (ca 1.45mm) 63
Figure 4.16: Velocity profiles in 1-pentanol (ca 1.85mm) 63
Figure 4.17: Velocity profiles in 1-hexanol (ca 1.45mm) 64
Figure 4.18: Velocity profiles in hexanol (ca 1.85mm) 65
Figure 4.19: Apparent terminal velocity (at 350mm) vs. concentration of 66
single bubbles in 1-butanol
Figure 4.20: Apparent terminal velocity (at 350mm) vs. concentration of 66
single bubbles in 1-pentanol
Figure 4.21: Apparent terminal velocity (at 350mm) vs. concentration of 67
single bubbles in 1-hexanol
Figure 4.22: Apparent terminal velocity (at 3000mm) vs. concentration 67
(ppm) of single bubbles for series of n-alcohols for ca. 1.45mm bubbles
Figure 4.23: Apparent terminal velocity (at 3000mm) vs. concentration 68
(mol/L) of single bubbles for series of n-alcohols for ca. 1.45mm bubbles
Figure 4.24: Apparent terminal velocity (at 3000mm) vs. concentration 68
(ppm) for ca. 1.45 and 1.85mm single bubbles in 1-pentanol and 1-hexanol
Figure 4.25: The terminal/apparent terminal rise velocity vs. bubble 70
diameter at 3000mm in the presence of MIBC, 1-hexanol and 2-hexanol
Figure 4.26: Velocity profiles in 2-hexanol (ca 1.5mm) 71
Figure 4.27: Apparent terminal velocity vs. concentration of single bubbles 71
in 1-hexanol, 2-hexanol and MIBC
Figure 4.28: Velocity profiles in MIBC (ca. 1.5mm) and NaCl (ca 1.6mm) 73

viii
Figure 4.29: The terminal/apparent terminal rise velocity vs. bubble 73
diameter at 3000mm in the presence of MIBC and NaCl
Figure 4.30: The terminal/apparent terminal velocity at 3000mm vs. bubble 75
diameter in the presence of the three commercial frothers
Figure 4.31: Apparent terminal velocity at 3000mm vs. concentration of 75
single bubbles in F150, DF250 and MIBC
Figure 4.32: The comparison of measured terminal rise velocity of MIBC 76
and Dowfroth 250 between the Sam et al. (1996) and the recent work
Figure 4.33: The influence of travel distance of bubble on critical 77
concentration and apparent terminal velocity in 1-pentanol for ca. 1.45mm
single bubbles
Figure 4.34: Comparison of terminal velocity of the used frother with clean 78
and contaminated water lines by Clift et al. (1978) (ca. 1.5mm)
Figure 4.35: Comparison of the trend line of current work with clean and 79
contaminated water lines by Clift et al. (1978)

ix
List of Tables
Table 3.1: Summary of reagents types and properties 44
Table 3.2: The equivalent concentrations of applied reagents 48
Table 4.1: The range of bubble size and frequency 49
Table 4.2: An example of measuring bubble size and calculating
54
measurement error

x
Nomenclature

A Area, m2 or cm2
BO Bond number
c Concentration of surfactant, mol/m3 or ppm
CD Drag coefficient
de Equivalent diameter of the bubble, mm or cm
E Aspect ratio
EO Eotvos number
FB Buoyant force
FD Drag force
Fr Froude number
g Acceleration constant, m/s2
H Bubble distance over the capillary, mm
Hl Liquid height
Jad Adsorption flux to the interface, mol/(m2.s)
Jdes Desprption flux from the interface, mol/(m2.s)
MO Morton number
mol Mole
Patm Atmospheric pressure
P0 Absolute pressure
R Gas constant, 8.314 N.m/(mol.K)
Re Reynolds number
t Time, s
T Absolute temperature, K
Ta Tadaki number
Ub Local velocity of bubble, cm/s
We Webber number
α Desorption rate constant, 1/s
β Adsorption rate constant, m3/([Link])
γ Surface tension of surfactant solution, N/m
γ0 Surface tension of water, N/m
Γ Surfactant concentration on bubble surface, mol/m2
Γ∞ Maximum surfactant concentration on bubble surface, mol/m2
μl Viscosity of liquid, N.s/m2
ρ Denssity, kg/m3 or g/cm3
ρl Liquid denssity, kg/m3 or g/cm3

xi
xii
CHAPTER ONE: INTRODUCTION
Particulate systems can be categorized on the basis of the phases involved: solid
particle, liquid and gas bubble. There are many wide industrial processes based
on two or three phase systems. It is important to understand the interactions to
optimize these processes. The complex nature of water requires special attention
to understand water-based two and three phase systems.

Bubble rise in liquids under different conditions is one of the oldest of scientific
investigations. It is of interest as the characteristics of a rising bubble (e.g. size,
shape, velocity and trajectory) give insight into the dynamics of a system. Rise
velocity is one of the most important characteristics of a rising bubble.

1.1. Single bubble rise velocity

Numerous studies have been performed on the motion of single bubbles. Clift et
al. (1978) reviewed the research prior to 1978. Kulkarani and Joshi (2005)
provide the most recent review on bubble formation and bubble rise velocity in
gas-liquid systems. There remain problems with some of the previous works
because of restrictions imposed by the experimental set-up and differences in
understanding the nature of bubble velocity especially in surfactant solutions.

The measurement of terminal velocity is a case in point: it is important to clarify

what velocity is being determined experimentally. Most studies report the
terminal velocity as an average velocity of a bubble over a given distance. Others
use the velocity at a fixed distance above the point of bubble release. Both
measures overlook a possible time-dependence of the velocity. This has led to
confusion over interpreting the impact of surfactant type and concentration.

Sam (1995) was one of the pioneers who applied an adjustable speed moving
video camera system to measure the velocity of a rising bubble as a function of
time or height, referring to this as the “velocity profile” (Sam et al., 1996). This
setup has opened a new approach to the fundamental study of the bubble motion

1
mechanism, as recognized by Dewsburry et al. (1999) and Kulkarani and Joshi
(2005).

In the presence of surfactant, depending on type and concentration, the velocity

profile (time-history) revealed three stages: acceleration, deceleration and
constant (terminal) velocity.

The common interpretation is that surfactants adsorb on the bubble and retard
the mobility of surface resulting in increased drag (Frumkin and Levich, 1947).
As the bubble rise and surfactant accumulates the corresponding increase in
drag can account for the three stages (Sam et al., 1996). Theoretically, the
velocity of a single bubble rising in surfactant solution can be solved by a
combination of the Navier-Stokes equation, mass transfer and the Marangoni
effect. These govern the fluid flow around the bubble, the amount of surfactant
on the bubble, and the extent of surface retardation and distribution of surfactant
on the surface, respectively. The surface retardation can be simulated by uniform
and stagnant cap models that determine rise velocity according to rate and
extent of accumulation of surfactant molecules on the bubble surface (Zhang et
al.., 2001; Zhang and Finch, 2002).

1.2. Velocity profile and terminal velocity of a single bubble

Sam et al. (1996) characterized the single bubble velocity profile by suggesting
three stages (Figure 1.1): first, a rapid increase to a maximum value
(acceleration); second, a decrease (deceleration); and third, a constant (terminal)
velocity stage. They observed the profile was strongly dependent on surfactant
type and concentration.

2
 Figure1.1: The stages of a typical velocity profile.

The different stages in the profile reflect different amount of adsorbed surfactant.
Initially the bubble surface is almost free of surfactant and the bubble accelerates
towards the velocity in a surfactant-free system. As surfactant molecules
accumulate drag increases and the bubble slows and eventually decelerates.
When adsorption reaches equilibrium (a steady state between adsorption at the
forward part of the bubble from where surfactant is swept by the flowing liquid
and desorption from the rear of the bubble to where the surfactants are swept)
the velocity of the bubble becomes constant considered as the terminal velocity.

According to Newton’s second law the terminal velocity of a body is the velocity
at which the body moves under a zero-acceleration condition. In the case of
terminal velocity of a bubble this indicates a balance between upward buoyancy
and downward drag forces.

Sam et al. (1996) reported that terminal velocity of a single bubble appeared to
depend on surfactant type but not surfactant concentration, only the time to reach
terminal velocity is affected. According to that conclusion, analysis of single
bubble terminal velocity vs. bubble size should reveal the influence of surfactant

3
type. Figure 1.2 presents the terminal velocity extremes, the trend for “clean” and
“contaminated” water (Clift et al., 2005).

Figure 1.2: Typical trend for terminal rise velocity in clean and contaminated water
(reproduced with permission from Clift et al. 2005).

While terminal velocity is an important property, the velocity profile can provide
further insight into surfactant action on bubble motion. This thesis will examine
velocity profile and terminal velocity of single bubbles in systems of interest in
mineral flotation.

1.3. Objectives of the study

The general objective is to use local rise velocity vs. distance (time) of single
bubbles (i.e., the velocity profile) to characterize systems of interest in flotation.
Some specific objectives include:
• Measure the velocity profile of some selected frothers, alcohols and salts
over a range of concentration and bubble size of interest to flotation (0.5-
2.5mm);
• Compare velocity vs. bubble size in 1-Pentanol (as a simple alcohol) and
F150 (as a polyglycol) to test the claim of frother type effect on velocity
presented by Azgomi et al. (2006);

4
 • Compare velocity vs. bubble size between MIBC (as a weak frother) and
NaCl (as a salt) to verify their common effect, according to the
observation of Quinn et al. (2007);
• Compare velocity vs. bubble size among some alcohols (C4-C8) to track
the effect of chain length;
• Compare single bubble results with recent swarms results (Acuna and
Finch, 2008).

1.4. Structure of the thesis

Chapter 1. Introduction: The gas/liquid system and parameters of bubble rise in
water are introduced followed by introduction to concept of velocity profile and
terminal rise velocity. The chapter ends by introducing objectives of the study
and structure of the thesis.

Chapter 2. Background and Literature Review: Required background

concerning forces acting and surfactant properties are presented. The literature
review begins with an introduction to bubble behavior and ends with more
detailed discussion on the impact of contaminants on bubble rise velocity.

Chapter 3. Experimental Setup: Here the experimental setup, methods,

measurement techniques and software are described.

Chapter 4. Results and Discussion: The results achieved toward each

objective are presented. Data are analyzed and compared with published works.

Chapter 5. Conclusions and Recommendations: The conclusions are

summarized and recommendations for future work entertained.

5
CHAPTER TWO: BACKGROUND

2.1. Bubble formation in gas-liquid systems

Some of the earliest studies on the formation of single bubbles were by Tate
(1864) and Bashforth and Adams (1883). A significant body of work on bubble
formation over a wide range of design and operational parameters has appeared
in the literature over the last few decades (Davidson and Schuler (1960), Tsuge
and co-workers, (1983, 1986, 1992, 1993, 1997, and 1999), Kumar et al.(1969),
Marmur et al. (1973, 1976), Vogelophl and co-workers (1982, 1986), Tan and co-
workers (2000, 2003).

A model of bubble formation from submerged orifice was proposed by Kumar et

al. (1969). Tsuge (1986) reviewed the hydrodynamics of bubble formation and
discussed various models. Rabiger and Vogelpohl (1986) discussed the various
factors affecting bubble formation. There have been several recent developments
in both numerical and experimental methods (Kulkarani and Joshi, 2005).

Bubble formation at a single submerged orifice can be classified according to the

following modes: low frequency bubbling, chain bubbling, wobbling and jetting.
These modes are dependent on the orifice configuration, the gas velocity, and
gas/liquid system properties.

2.2. Theoretical aspects

2.2.1. Forces
Particle (defined generally to include solid, liquid (droplet) or gas (bubble)) motion
in a liquid is controlled by forces that act on the particle. The fundamental
aspects are based on Newton’s second law illustrated by the momentum “Navier-
Stokes” equation.

6
The motion of a bubble in a liquid is subjected to buoyancy and drag forces and,
because there is a different cohesive force between water and air molecules, an
interfacial force also appears, surface tension. The forces are briefly described.

[Link]. Surface tension

The Navier-Stokes equation can be considered as a general force balance for a
fluid in motion. When an interface is involved (e.g., bubble/water interface), an
interfacial (or surface) tension force is present. The interface behaves like a thin
stressed membrane under tension (Eskinazi, 1968).

Surfactant and salts affect the surface tension of the air/water interface, the
former reducing surface tension the later often increasing surface tension. The
surface tension may be a function of time called dynamic surface tension (Defay
and Prigozine, 1960). That feature is recognized to have a role in some flotation
systems (Defay and Prigozine, 1960; Finch and Smith, 1972; Kulkarani and
Somasundaran, 1975; Leja, 1982; Comley et al. 2002). The equilibrium surface
tension of an air/water interface depends on the quantity of adsorbed molecules
of surfactant. Above a certain concentration of surfactant, the surface tension
becomes constant and any surfactant forms colloidal aggregates within the bulk
solution known as micelles where CMC stands for critical micelle concentration.

[Link]. Buoyancy
According to Archimedes’ principle a particle whose average density is less than
that of the liquid floats on that liquid. The direction of the buoyancy force for both
falling (object has higher density than water) and rising (object has lower density
than water) motion in water is upward. For a sphere the buoyancy force FB, is
determined by:

πd e3 ρ l g
FB = (2-1)
6
where, de and ρl, are particle equivalent diameter and liquid density, respectively.

7
In bubble motion analysis, it is usually assumed that because the density of air is
very small the gravitational force is negligible.

[Link]. Drag
Drag force is defined as the resultant of the forces acting to resist motion of a
particle in a liquid; on a bubble rising through a liquid the direction of this force is
downward. For a bubble in motion relative to liquid, a skin (viscous or shear) drag
will exist between the bubble surface and the fluid. The drag comes from the
friction of the fluid on the bubble surface and demonstrates itself as the viscous
force in the Navier-Stokes equation even if viscosity is very low (Binder, 1973).

During motion of a bubble the liquid passes over the bubble and the flow
separates at some point on the rear half of the bubble. Thus a pressure
difference occurs between the separated and non-separated flow regions. By
considering a pressure difference on a projected area of a bubble, a drag force
called pressure or shape drag is derived.

The drag coefficient (CD) is a dimensionless quantity which is used to describe

the drag force. The total drag force can then be expressed as:

ρ lU b2
FD = C D A (2-2)
2
where, ρl, Ub and A are liquid density, bubble local rise velocity and area,
respectively.

According to the dependency of the drag force on the bubble shape and
Reynolds number, it is normally presented as a plot of Reynolds number vs.
particle shape (Massey, 1983).

2.2.2. Force ratio

Dimensionless analysis is a tool for checking equations and units, determining a
convenient arrangement of physical variables and planning systematic
experiments (Binder, 1973). Since physical laws express natural phenomena,

8
they are independent of the units of the dimensions used; thus it is possible to
express the laws in dimensionless form.

Dimensionless groups arise from dynamic similarity (Massey, 1983). If two

systems are dynamically similar then the magnitude of forces at similarly located
points in each system are in a fixed ratio. Consequently, when the ratio of forces
acting on a fluid particle in one case is the same as the ratio of those forces at a
corresponding point in another case, then mechanical similarity is realized
(Binder, 1973). In general, the similarity of flow depends not only on one ratio of
forces, but on two or possibly three ratios.

The dimensionless groups which have usually been considered in bubble motion
analysis are1:

inertia force ρ l U b2 d e
Re (Reynolds No.) = = (2-3)
viscous force μl

inertia force ρ U 2d
We (Webber No.) = = l b e (2-4)
surface tension force σ

gravity force gρ l d e2
Eo (Eotvos No.) = = (2-5)
surface tension force σ

inertia force U b2
Fr (Froude No.) = = (2-6)
gravity force d e g
1/ 2
⎡ gρ ⎤
Bo (Bond No.) = Eo 1/ 2
= de ⎢ l ⎥ (2-7)
⎣ σ ⎦

gμ l4
Mo (Morton No.) = (2-8)
ρ lσ 3
3/ 4
⎛ ρl ⎞
Ta (Tadaki No.) = g 1/ 4
⎜ ⎟ d eU b (2-9)
⎝σ ⎠

1
See nomenclature for definition of symbols

9
2.2.3. Wake phenomenon
It is known that the rise characteristics of bubbles in liquid, such as shape, rise
velocity and oscillations are closely related to the bubble wake behavior
(Tsuchiya and Fan, 1988). The wake structure is dependent upon several
factors including: particle geometry, size and nature of the particle surface;
relative motion between the particle and surrounding medium; and the physical
properties of particle and liquid.

Vannard and Street (1975) characterized wake phenomenon as a function of

Reynolds number (Figure 2.1). At Re<1 there is no wake. As Re increases at a
certain Re (about Re ≈ 20), the flow starts to separate from the particle surface.
This critical Re is dependent on particle shape, particle surface nature and the
turbulence intensity in the surrounding media. As the Reynolds number increases
from the critical value, the separated streamlines branch off from the particle
contour. This creates a closed region behind the particle called the “wake or
circulation region” (Figure 2.1).

The wake structure for bubbles is known to differ from that for solid particles, due
to bubble oscillation or rocking under the influence of asymmetric vortex
shedding at least for bubbles ≥1.5mm. Bhaga (1976), Clift et al. (1978), Bhaga
and Weber (1980, 81), Weber and Bhaga (1982), Tsuchiya and Fan (1988),
Kreischer et al. (1990) and Fan and Tsuchiya (1990) among others have
investigated bubble wake phenomena. They discussed the bubble wake
structure and geometry, circulation flow pattern in the bubble wake and bubble
wake instability for different bubble sizes and shapes or, generally, for different
Reynolds numbers.

The wake volume is a function of Reynolds number and the ratio of the wake
volume to the bubble volume increases with increasing Reynolds number (Bhaga
and Weber, 1981). George et al. (2006) report an empirical correlation for
volume.

10
 Figure 2.1: Circulation region (wake) behind a sphere at various Reynolds numbers
(Vennard and Street, 1975).

2.3. Surfactants and their influence at air/water interface

2.3.1. Surfactant and frother

A surface active agent or surfactant is a compound that in very small quantities is
able to change the properties of a surface, often with little to no influence on any
other properties. A surfactant’s surface activity is most widely encountered in the
lowering of surface tension of water (Tsujii, 1997).

Surfactant structure consists of a polar group with a hydrocarbon chain, i.e., they
belong to the mixed hydrophilic/hydrophobic structural class. By residing at the

11
interface with the polar part in the water and the hydrocarbon chain in air both the
hydrophilic and hydrophobic properties are satisfied simultaneously.
Consequently, surfactant accumulates at the interface.

Frothers, the reagents added in most flotation systems to control bubble related
properties, are surfactants. Most frothers are based on alcohols and polyglycols.
Their main tasks are to reduce bubble size and promote froth stability

2.3.2. Surfactant adsorption mechanism

The exchange rate of surfactant between the bulk solution and interface is a
function of surfactant concentration and surface activity. Two mechanisms,
diffusional transport and non-diffusional adsorption, govern the exchange rate.
For highly surface active (or strong) surfactants, i.e., those for which rate of
surface tension decrease with concentration is high, the exchange rate is
controlled by diffusional transport if the concentration is low. For weak
surfactants and comparatively high concentrations of strong surfactants, non-
diffusional adsorption kinetics govern (Bleys and Loos, 1985; Fainerman, 1985).

The Langmuir adsorption model is one of the first and most important models.
Here, the adsorption rate is described as a balance of surfactant adsorption flux
to the interface (Jad) and desorption flux from the interface (Jdes):
dΓ
= J ad − J des (2-10)
dt

The Langmuir model can be presented as:

dΓ
= βc(0, t )(Γ∞ − Γ ) − αΓ (2-11)
dt

For most surfactants non-diffusional adsorption kinetics can be expected if the

Langmuir-Von Szyskowski constant (a = α/β) is larger than 1 mol.m-3 (Fainerman
et al., 1998).

12
When equilibrium is reached the Gibbs adsorption isotherm relates the surfactant
excess concentration on the interface to the surface tension:
1 dγ
Γ=− (2-12)
RT d ln c
Combining with the Langmuir adsorption isotherm gives:
Γ
γ 0 − γ = − RTΓ∞ ln(1 − ) (2-13)
Γ∞
where γ0 is the surface tension of water. If the surfactant concentration is very
Γ
low, would be close to zero and the Langmuir isotherm can be simplified to:
Γ∞

γ 0 − γ = RTΓ (2-14)

In the other words in this situation there is a linear dependency between surface
tension and surface concentration (or adsorption density). Frumkin (1925)
introduced additional interaction forces between adsorbed molecules into the
Langmuir adsorption isotherm.

2.3.3. Surfactant distribution

Dukhin et al. (1995) reviewed developments in the theory, and experimental
aspects of surfactant adsorption at a liquid interface. One of the models of
surfactant distribution between interface and bulk solution is shown schematically
in Figure 2.2.

According to Figure 2.2 the air/water interface is divided into three regions: the
interface, where the surfactant molecules accumulate; the sublayer that is
adjacent to the interface and is in equilibrium with the interface at all times; and
the bulk solution that has a uniform concentration of surfactant. Here the
transport of surfactant from bulk solution to the interface occurs by migration of
surfactant from the bulk to the sublayer, followed by its adsorption at the
interface.

13
 Figure 2.2: Accumulation of surfactant at air/water interface (after Dukhin et al., 1995).

The distribution of surfactant over the bubble surface is governed by the

adsorption kinetics and transport properties of the surfactant. The nature of the
adsorbed layer at the interface can be characterized by two extremes: soluble
and non-soluble. If the surfactant flux from the bulk is extremely slow compared
to surface convection, the adsorbed surfactant behaves as an insoluble
monolayer. At this extreme the interface can be divided into two zones, the
leading zone, which is mobile and swept free of surfactant, and the trailing zone
which has a high surfactant concentration and is considered stagnated (Cuenot
et aI., 1997). The size of this stagnant region is specified by a cap angle (θ)
measured from the trailing pole to the edge of the stagnated zone. At the
opposite extreme, when the surfactant flux from the bulk is only slightly less than
the surface convective flux, a smoothly changing concentration gradient develops
over the entire surface. The bubble surface can then be classified into four cases
according to the surface velocity: the unretarded surface; the uniformly retarded
surface; the partly stagnated surface; and the completely stagnant interface.
Figure 2.3 shows the distribution of surfactant and surface velocity (US) on the
bubble for the two extremes of the adsorption layer.

14
 Figure 2.3: Surfactant and velocity distribution on bubble surface for the two
extremes (Cuenot et al., 1997).

The uniformly retarded surface model has been considered by many researchers
(Levich, 1962; Schechter and Fairley, 1963; Newman, 1967; Harper, 1972; He et
al., 1991). However, stagnant cap model is considered appropriate in most
cases (Savic, 1953; Garner and Skelland, 1955; Elzinga and Banchero, 1961;
Griffith, 1962; Horton el aI., 1965; Huang and Kintner, 1969; Beitel and
Heidegger, 1971; Yamamoto and Ishii, 1987).

2.3.4. Some consequences of presence of surfactant at air/water interface

[Link]. Marangoni effect

Natural convection due to density differences and Marangoni convection due to
an interfacial tension gradient at the free interface of the fluid (Marangoni effect)
can occur spontaneously (Okano et al., 1989; Bergman and Webb, 1990;
Gaskell, 1992; Lan and Kou, 1992).

In an isothermal system the Marangoni effect can be explained as follows. After

releasing a bubble into water that contains surfactant, the surfactant adsorbs at

15
the air/water interface. But the motion of the bubble sweeps the adsorbed
surfactant molecules from the front of the bubble to the rear; i.e., provides a non-
uniform distribution of surfactant (Figure 2.4). Therefore, the concentration of
surfactant at the rear is larger than that at the front. This non-uniformity induces a
surface tension gradient toward the front of the bubble which subsequently
generates a tangential shear stress that retards the surface velocity and
increases the drag coefficient. This phenomenon is called the Marangoni effect
(Frumkin and Levich, 1947; Levich 1962).

Figure 2.4: The distribution of adsorbed surface active solute on the surface of a
rising bubble (Linton, 1957).

One consequence is a reduced bubble rise velocity because of the increase in

drag coefficient. Another consequence is the bubble attains a more spherical
shape, the shear stress opposing the force resulting from the pressure drop
across the bubble which causes it to flatten. The bubble is said to become more
“rigid”.

In a non isothermal system the convection direction is from the hot to the cold
region. Density and surface tension are lower on the hot side and, consequently
Marangoni convection again occurs.

16
[Link]. Interaction between surfactant and water molecules
In addition to surface tension gradient driven phenomena the interaction between
the polar group and water molecules via H-bonding can also be a factor
controlling bubble motion. Water molecules can be seen as traveling with the
bubble and retarding the bubble rise through an increase in surface viscosity. It is
the combination of interaction with water molecules and the surface tension
gradient effect that increases the drag on the bubble according to some
(Fuerstenau and Wayman, 1958; Leja, 1982; King, 1982; Crozier, 1992; Urry,
1995). In a similar vein Malysa et al. (1988) reported that long chain polymers
could reduce the settling velocity of colloidal particles significantly, which was
attributed to interaction with water molecules.

By introducing this chemical aspect an effect of surfactant type as well as

concentration is anticipated which is not so readily associated with the physical
properties due to surface tension phenomena.

[Link]. Effect on bubble internal circulation

There are a few studies on bubble internal circulation (Hadamard and
Rybczynski, 1911; Garner and Hammerton, 1954; Linton and Sutherland, 1957;
Griffith, 1962; Lochiel, 1965; Clift et al., 1978). As the internal circulation depends
on the mobility of the surface, the properties of the interface and the effect of
surfactants play a significant role.

For a moving bubble any part of the surface experiences a tangential force
proportional to the viscosity of the external medium. The circulation pattern is
dependent on the fluid properties, and size and shape of the bubble (Linton and
Sutherland, 1957).

Schechter and Farley (1963) considered the circulation as resulting from the air
inside the bubble near the interface being swept from the leading end to the rear
by the action of the flowing liquid inducing stress on the interface. At the rear of

17
the bubble air flowing along the interface is then forced into the interior of the
bubble and the circulation pattern is established.

If due to presence of surfactant the surface becomes sufficiently rigid the internal
circulation decreases. In the other words, an opposing force to circulation is
introduced if the interfacial tension varies over the surface. If the adsorption-
desorption process of surfactant is fast the surface tension will be almost
constant over the surface and the resultant surface tension gradient would be
small. Oppositely, if the adsorption-desorption process is slow higher surface
tension gradients would be produced. The modes of internal circulation are:
complete circulation, part circulation, and stagnant (Figure 2.5).

Figure 2.5: The internal circulation of moving fluid showing the direction of relative flow: (a)
complete circulation, (b) part circulation, (c) stagnant (Linton, 1957).

According to Figure 2.5 complete circulation occurs in pure liquids and fully
stagnant mode can be achieved as a result of a large enough surface tension
gradient. In general, the internal circulation is governed by the velocity, pressure
drop across the bubble and time dependent surface tension gradient in the
bubble surface. One consequence is that larger bubbles experience more
internal circulation.

18
2.3. Bubble behavior
Bubble rise in liquids has been investigated over many decades. In the early
work it was assumed that the fluid surrounding the bubble has zero viscosity, and
there is no slip at the boundary (Lamb, 1954). But for real fluids the situation is
more complex because the gas bubble does experience slip and viscous and
inertial forces are present.

The regimes of bubble motion in liquid can be classified as Stokes regime,

Hadamard regime, Levich regime, and Taylor regime (Astarita and Apuzzo,
1965). The characteristics of a rising bubble (i.e., its size, rise velocity, trajectory,
etc.), differ from system to system, making it difficult to develop generalized
correlations. To understand bubble behavior fundamental analyses have been
performed from different points of view (Auton, 1987; Eames & Hunt, 1997;
Magnaudet & Eames, 2000; Mei and Klausner, 1992). However, the most usual
approach is through the force balance.

Many investigators (Astarita, 1996; Davis and Acrivos, 1996; Haque et al., 1987;
Clift et al., 1978; Abou-ElHassan, 1983; Chhabra, 1993; Gummalam, 1987;
Rodrigue, 2001, 2002) have worked extensively in various gas-liquid systems
and developed correlations for a specific range of conditions. It seems the recent
attempts by Nguyen (1998) and Rodrigue and co-workers (1996, 2001, 2002,
2004) to develop a generalized correlation can be considered applicable over a
wide range; still, important deviations remain to be incorporated.

Single bubble rise characteristics depend on the bubble generation system and
the force acting. Figure 2.6 describes the connections among various factors.
Examination of these parameters can provide an indirect understanding of the
forces acting and their consequences.

19
 Gas/Liquid system:
-Gas: type, temperature, saturation, solubility, density
-Liquid: density, temperature, type, purity, surface
tension, viscosity
-Orifice: Type, size, direction, material
-Column: size
-Surfactant: type, concentration, surface tension
-Bubble Generation: gas rate, frequency, system geometry

Bubble Behavior:
-size Forces:
-velocity -buoyancy
-shape -drag
-path -surface tension

Consequences:
-surface mobility
-wake
-internal circulation
-Marangoni effect
-surface tension gradients

Figure 2.6: The relationships between identified factors that affect bubble behavior.

2.31. Bubble size

The surface mobility of a bubble provides for variable shape during its rise in a
liquid. It is then convenient to define an equivalent diameter (de), namely:
d e = ( x. y.z )
1/ 3
(2-15)

where, x, y and z are diameters in the X, Y, Z directions.

20
For a spherical bubble these diameters will be similar and for a flattened bubble
(oblate spheroid), Δy, for instance, will be less than Δx. Aspect ratio (E) is the
ratio of minor to major axis. If aspect ratio is close to 1 (0.9>E>1) the object can
considered as spherical (Clift et al., 1978).

Bubble size is changed by hydrostatic pressure. In a static fluid, shear and

tensile forces are absent, and the only force involved is a compressive one.
According to Pascal’s law the pressure in a static fluid is the same in all
directions. The absolute pressure (P0) is given by equation:

P0 = Patm + ρghl (2-16)

where Patm is atmospheric pressure and hl is the height of liquid over the bubble.

As a bubble rises through a column the height of liquid above and therefore
pressure on the bubble decreases. Assuming the ideal gas law and an
isothermal system the bubble size increase during rise in a liquid can be
calculated.

2.3.2. Bubble shape

The interaction between a rising bubble and the surrounding liquid medium
determines the bubble shape and the extent of the disturbance in the
surrounding flow field (Fan and Tsuchiya, 1990). Bubbles in motion can be
classified by shape as spherical, ellipsoidal and spherical/ellipsoidal cap. De
Vries (2001) summarized the results of previous work for shape of bubble and
onset of shape oscillations.

For single small bubbles (e.g., de<1mm), bubble shape is approximately

spherical. When bubble size increases dynamic, viscous and inertial forces come
into play. The dynamic pressure due to the flow decreases along the bubble
surface from the bubble front to the sides. Thus with increasing bubble size (or

21
Re), the dynamic pressure between the bubble front and bubble side increases
which explains why the bubble flattens (ellipsoid oblate shape) in the direction of
the bubble motion. Addition of surfactant by introducing surface viscosity and
surface tension effects can reduce the effect of dynamic pressure difference on
flattening; i.e., increases the aspect ratio of the bubble (Figure 2.7).

Figure 2.7: Illustration of dynamic pressure causing bubble deformation in water only case
(a), and the force created by surface tension gradient that occurs in presence of surfactant
that resists deformation (b) (Finch et al., 2008).

For large bubbles (de>18mm) (Clift et al., 1978) the effect of surface tension and
viscosity are negligible and inertial or buoyancy forces are dominant and the
bubble shape is ellipsoidal/spherical cap. The induced pressure difference
between the front and the side of the bubble explains the transition of bubble
shape from spherical to ellipsoidal but it is not enough to describe the transition
of ellipsoidal to spherical/ellipsoidal cap.

Haberman and Morton (1953) suggested that a dimensional analysis for

prediction of bubble shape can be based on the acceleration due to gravity, the
terminal velocity of bubble rise, the diameter of volume equivalent sphere, the
liquid density and viscosity and finally the interfacial tension. These variables
appear in three dimensionless numbers: Reynolds, Morton and Eotvos. Figure

22
2.8 shows the shape regimes and bubble shape transition boundaries for
bubbles in motion through liquids (Clift et al., 1978).

Generally, for a given size of bubble it becomes less flattened when the liquid
surface tension is large (low We or Eo) and the liquid viscosity is large (low Re).
But when the system is contaminated, by surfactant molecules that collect at the
liquid-bubble interface the bubble shape cannot be determined by liquid
properties alone. In other words, the bubble shape is strongly influenced by the
conditions at the gas/liquid interface (Griffith, 1962; Grace et al., 1976). By
adsorption of surfactant at the interface, the viscous drag increases (Boussinesq,
1913; Sciven, 1959; Agrawal and Wasa, 1979; Fan and Tsuchiya, 1990).

Figure 2.8: Bubble shape regime (reproduced with permission from Clift et al., 1978).

23
2.3.3. Bubble rise path
The bubble rise path can be defined by the trajectory of the bubble centre. Fan
and Tsuchiya (1990) note that the bubble rise path and change in orientation
(defined as the angle between the bubble major axis and the vertical axis of the
system) are strongly dependent on the bubble shape. De Vries (2001)
summarized the path instability modes and the regimes observed.

Single bubbles rise in a straight line (rectilinear) when they are spherical. On
increasing bubble size the bubble starts to deform into an ellipsoidal shape and
the bubble starts to exhibit zigzag or spiral motion. Bubble orientation is also
affected by shape deformation (Tsuge and Hibino, 1977; Fan and Tsuchiya,
1990). As the bubble changes from ellipsoidal to spherical/ellipsoidal cap (at Re
≈ 5000 (Miyahara, 1988)), the radius of the spiral or the amplitude of the zigzag
decreases and the motion becomes rectilinear, but with rocking.

The bubble rise path and fluctuations in the orientation of the bubble can be
characterized by the frequency or period of cycle of the motion according to
Tsuge and Hibino (1971). In general, both the amplitude and frequency of bubble
oscillation are related to the bubble size, shape and presence/absence of
surfactants.

Detailed experiments were discussed by De Vries et al. (2002), who investigated

the motion of gas bubbles in highly purified water. For bubble size <2mm, the
bubbles rise axisymmetrically. Shape oscillation for bubble size >2mm was
observed at a certain height depending on the conditions and especially bubble
size. In this situation bubbles establish an approximately ellipsoidal shape.

Typically, the dynamics of bubble rise is nonlinear and the extent of nonlinearity
increases with bubbles size. Observations have shown that bubble trajectories
have a primary and secondary structure (Yoshida and Manasseh, 1997). For
high viscosity Newtonian and non-Newtonian liquids, irrespective of the size of

24
the bubble the trajectories are rectilinear, mainly because of the large viscous
drag.

Lunde and Perkins (1997) clarified the relationship between the wake structure
and trajectory of clean bubbles (helical or zigzag). They suggested that there
may be a correspondence between the wake structure and the bubble trajectory.

2.3.4. Bubble rise velocity

After the detachment of a bubble from an orifice under a liquid, the buoyant force
causes it to rise. The dynamics associated with the rise are mainly due to
temporal variation in bubble characteristics.

Measurement of bubble rise velocity is important in order to understand, for

example bubble dispersion in a liquid and the adsorption mechanism at a
gas/liquid interface. Rise velocity is fundamental to the performance of bubble
reactors.

To discuss rise velocity of a bubble two terms are introduced: local and terminal
velocity. Local velocity is the velocity of a rising bubble at a certain time or
distance after release. Terminal velocity is the velocity of a bubble when
according to the Newton’s second law acceleration is zero. In other words, it
represents the constant velocity of the rising bubble when time no longer
influences local velocity significantly. Figure 1.1 showed the terminal velocity as
the third stage of the velocity profile (Sam et al., 1996). (In reality the bubble will
increase in size as it rises due to decreasing hydrostatic pressure and velocity
will change in a predictable manner (e.g. see Zhang et al. (2003)).

The rise of a bubble in a liquid can be considered as a function of several

parameters including: bubble characteristics (size and shape); properties of the
gas-liquid system (density, viscosity, surface tension, concentration of solute,
density difference between gas and liquid); liquid motion (direction); and

25
operating conditions (temperature and pressure). Some of these will be
described with regard to their importance as established in many studies.

[Link]. Factors affecting the rise velocity

a- Type and purity of liquid
The rise velocity in each pure liquid would be different. However, the same trend
may be observed. Kulkarani and Joshi (2005) presented bubble rise velocity for
some pure and contaminated liquids.

In Figure 2.9, bubble terminal rise velocity vs. size is shown for an inviscid water.
Here the upper bound of the terminal velocity data is considered to correspond to
bubbles in pure water while in the presence of surfactant, the drag force
increases and consequently causes a reduction in velocity leading to the scatter
in the data (Clift et al., 1978; Fan and Tsuchiya, 1990). The influence of
surfactants on bubble rise velocity will form a large part of this review. The results
for fully contaminated water give the lower part of the data envelope.

b- Liquid viscosity
The modes of bubble rise show distinct behavior in viscous Newtonian fluids
compared to inviscid and non-Newtonian liquids (Gonzaleztello et al., 1992).
Rodrigue et al. (1996) reported an almost linear relationship between rise velocity
and the bubble volume dependent on the liquid viscosity.

For the case of different non-Newtonian liquids, viscosity influences the

relationship between the bubble size and rise velocity. For instance, terminal rise
velocity may exhibit a discontinuity at a certain critical bubble size in some
liquids, while no discontinuity is observed for some others. Leal et al. (1971),
Astarita and Apuzzo (1965), Acharya et aI. (1978), and Rodrigue (1998) have
investigated this phenomenon in detail.

26
c-Temperature
According to the ideal gas law, at constant pressure the bubble volume increases
with increasing temperature and as a consequence bubble rise velocity may
change (depending on the initial size).

Figure 2.9: Typical trends in rise velocity with bubble size for pure and
contaminated liquids (Kulkarani and Joshi, 2005).

Figure 2.10: Effect of initial bubble deformation on terminal velocity in distilled

water (Kulkarani and Joshi, 2005).
\

27
In addition liquid density is inversely proportional to the temperature variation,
which influences buoyancy and thus rise velocity. However, this effect is not
significant when compared to other physical properties of the liquid that affect the
bubble rise velocity.

There are few studies on the effect of temperature on rise velocity of a bubble. At
ambient conditions, the rise velocity follows a certain trend with bubble size. Here
two different cases may be considered: rise of a gas bubble that is insoluble in
the liquid and rise of vapor bubble in liquid at relatively low temperature. Both
cases are common, while only the second case has been studied systematically.
In the first case the heat transfer across the interface causes an increase in
bubble volume. Also, at higher temperature the density difference between the
two fluids decreases. Hence the buoyancy decreases and this reduces the rise
velocity. The counteracting effects are dominant in different ranges of
temperature and in a certain temperature range rise velocity is a strong function
of size.
Zhang (2000) and Zhang et al. (2003) reported a temperature effect on single
bubble velocity profile in water and surfactant solution. The profiles indicated that
the time to reach constant velocity tended to decrease as temperature increased.

d- External pressure
Although most laboratory scale investigations of bubble dynamics are carried out
at ambient conditions, the operating conditions in industrial systems are often
significantly different (e.g. at elevated pressure). As a result of the outside
pressure, bubbles are formed only after a minimum gas velocity is reached
(which is higher than under ambient conditions), while the bubble sizes are
smaller (subsequently reducing rise velocity). Letzel (1998) systematically
analyzed the effect of gas density on the rise velocity of large bubbles. In a
similar attempt, under the assumption of homogeneous nature of the suspension,
Luo et al. (1997) studied the effect of external pressure on bubble rise velocity in
a gas-liquid-solid fluidized bed (Newtonian viscous system). Increased pressure

28
was found to have less effect at higher temperatures, mainly because the
difference between the vapor pressure of liquid and external pressure is
decreased.

e- Initial bubble detachment condition

According to Figure 2.9 and the accompanying discussion concerning purity, the
scatter has been related to the concentration of contaminants. But according to
Tomiyama et al. (2001, 2002) and Wu and Gharib (2002) another reason for this
scatter is the way the bubble is released from the orifice; i.e., the initial condition
at detachment.

According to their analysis, for low initial shape deformation, bubble rise is at a
lower velocity with a trajectory following either a rectilinear or zigzag path. For
large initial shape deformation terminal velocity is high and produces wide scatter
depending on the different possible release conditions and deformations. This
scatter is depicted in Figure 2.10.

Tomiyama (2004) has shown that Figure 2.9 is comprised of data points that can
be bounded with three drag curves. For a bubble having constant equivalent
diameter an increase in aspect ratio, i.e., shape approaches a sphere, is shown
to reduce terminal velocity. Kracht (2008), reported the same observation.

f-Gas type
There are few studies into the influence of gas type on rise velocity. Parkinson et
al. (2008) studied the influence of some gasses on the terminal rise velocity of 1-
100μm diameter bubbles in water. For N2, He and air bubbles, excellent
agreement with the Hadamard-Rybczynski equation was observed, indicating
that slip was occurring at the liquid/vapor interface. For CO2 bubbles terminal rise
velocity was higher than other gasses examined, attributed to its higher solubility
compared to the other gasses (Parkinson et al., 2008).

29
Zhang (2000) examined the influence of gas saturation (humidity) on terminal
velocity. In general, air (as a gas) is able to absorb a certain amount of moisture.
In that study the air was first fed through a water container to become saturated
by water. The saturated air was fed to a column to generate bubbles. The results
indicated that there was no significant difference between fresh and moisture
saturated air bubbles.

2.3.5. Formulation for rise velocity correlation

Several investigators have developed empirical, semi-empirical and theoretical
simulations for bubble rise velocity. Most apply only for a narrow range of
governing parameters. In the review by Kulkarani and Joshi (2005) some rise
velocity models were based on the following: force balance, dimensional
analysis, and wave analogy. They listed many formulae for rise velocity in
Newtonian and non-Newtonian liquids.

2.4. Contaminants and rise velocity

As the main purpose of this research is focused on the effect of frother
(surfactant) on single bubble rise velocity, this will naturally occupy a significant
part of the review. In addition to the effects of frother, the role of salts is included
as, for some functions, frother and some salts are interchangeable.

2.4.1. Surfactant
According to Figure 2.9 at ambient conditions the velocity increases with size and
passes through a maximum at ca 1.3mm (diameter) followed by a decrease in
velocity over a restricted size range after which it attains a weakly positive
dependence on bubble size. Depending upon the type and concentration of
contaminant, the rise velocity characteristics of a bubble change significantly.
The impact of surfactants on bubble rise velocity is reviewed according to liquid
rheological class.

30
[Link]. Newtonian liquids
In a Newtonian liquid the non-uniformly distributed adsorbed surfactant
generates a surface tension gradient. Since the surface tension gradient must be
balanced by a jump in the shear stress across the interface (Marangoni effect), a
shear-free boundary condition can no longer be imposed on the liquid at the gas-
liquid interface. So this leads to an increase in the drag force (stagnant cap
hypothesis). As a result of formation of a rigid interface and enhancement in
drag, internal circulation is reduced and the rise velocity is lower than in the clean
(surfactant-free) liquid. The stagnant cap hypothesis has been used successfully
for the estimation of bubble rise velocity and has also been used for the
prediction of drag coefficient with respect to extent of surface contamination.

Frumkin & Levich (1947) and Levich (1962) developed a so-called adsorption
theory to explain the reduction in rise velocity. Savic (1953) reported the
existence of a cap (surface immobilization) on the rear part of a moving liquid
drop, while the rest was tangentially stress free (mobile). Griffith (1962) studied
the effect of surfactant on the terminal velocity of drops and bubbles. Kopf-Sill
and Homsey (1988) applied the Hele-Shaw cell model to analyze the effect of
surfactants. Fdilha and Duineveld (1995) investigated the effect of surfactant on
the rise of a spherical bubble at high Reynolds and Peclet numbers. They found
that the rapid slowdown of the bubble occurs when nearly half of the bubble
surface is covered by the surfactant layer. De Kee et al. (1990) reported that a
reduction in surface tension resulted in a decrease of bubble rise velocity of small
bubbles without any discontinuity. However Rodrigue et al.(1996) reporting the
same phenomenon, found no influence on bubble rise velocity over a certain
concentration of surfactant. Cuenot et al. (1997) discussed how retardation of the
bubble surface fluidity is dependent on the amount of adsorbed surfactant. Sam
et al. (1996) studied axial velocity profiles of single bubbles in water/frother
solutions and among other findings concluded there was no concentration effect
on terminal velocity only on the time to reach terminal velocity. Zhang and Finch
(2000) confirmed that terminal rise velocity was independent of concentration on

31
concentration for the surfactants tested. Krzan et al. (2004) studied the influence
of the surfactant polar group on the local and terminal velocities of bubbles. Here
the minimum adsorption coverage required to immobilize the bubble surface was
estimated for some surfactants. They concluded that mainly surfactant
adsorption kinetics governed the mobility of rising bubble interfaces. Recently,
Acuna et al. (2008) reported that the frother type could affect the terminal
velocities of same size bubbles in swarms, even for diameters below 1mm.

[Link]. Non-Newtonian liquids

Rheological behavior of non-Newtonian liquids is complex and the motion of
bubbles in these liquids has different characteristics to those observed in
Newtonian liquids. For the case of power-law non-Newtonian liquids, Tzounakos
et al. (2004) studied the effects of surfactants based on analysis of the drag
curve. Ybert and Di Meglio (1998) measured bubble rise velocity as a function of
distance traveled. After the initial stage of acceleration from rest, the
instantaneous rise velocity of a given bubble depended only on the total amount
of surfactant adsorbed on the bubble surface. It was also shown that the
surfactants are not only absorbed onto the bubble surface, but may also desorb,
which increases the bubble rise velocity.

[Link]. High viscosity liquids

The few studies (Barnett et al.,1966; Haque et al., 1988; Margaritis et al.,1999;
Miyahara and Yamanaka, 1993 and De Kee et al., 1986) have shown that for
high viscosity Newtonian liquids, the rise velocity is a weak function of the bubble
volume, while for non-Newtonian liquids, it has a linear dependence but the
velocities in the former case are much higher than in the latter.

[Link]. Simulation and numerical analysis

There are several published simulations and numerical analyses of bubble rise
velocity in the presence of surfactant. Some that directly discuss terminal velocity
are: Harper (1973 and 1987), Fdhila and Duineveld (1995), McLaughlin (1996),
Nguyen (1998), Rodrigue et al. (1999), Liao and McLaughilin (2000), Bozzano

32
and Dente (2001), Zhang et al. (2001), Alves et al. (2005), Liao et al. (2004) and
Takemura (2005).

2.4.2. Frothers
In the present context the action of frother is to retard bubble rise velocity. There
have been few studies on single bubble rise velocity in the presence of frothers.
Sam et al. (1996) added trace amounts of MIBC, pine oil and Dowfroth 250 to
water and studying the velocity profile over some 400cm found that the profile
was sensitive to frother type and concentration, but while the terminal velocity
appeared dependent on frother type, it was not dependent on frother
concentration. The time-dependent velocity was attributed to time dependent
adsorption of surfactant causing increased bubble rigidity and surface viscosity.
Figure 2.11 shows the velocity profiles for 2.2mm bubbles in MIBC (a) and
terminal velocity vs. bubble size for some frothers (b).

Zhang (2000) and Zhang and Finch (2000) studied the impact of MIBC, pine oil,
Dowfroth 250 and Dowfroth 1263 on the rise velocity of single bubbles. These
results confirmed the previous study by Sam (1995). It was noted that the
distance to reach terminal velocity in surfactant solution was dependent on
bubble size, surfactant type and surfactant concentration. A good agreement was
achieved between measured terminal velocity in these solutions and
Karamanev’s model for Re>130 (Karamanev, 1994). For Re<130 it was shown
that when a bubble reaches terminal velocity, the bubble surface can be
reasonably set as a no-slip boundary condition.

Krzan and co-workers report velocity profiles for 1-butanol and 1-hexanol (Krzan
and Malysa, 2002), and 1-pentanol and 1-octanol (Krzan et al., 2007) at 40 and
350mm distance over a capillary tip. It was reported that at low concentrations of
the alcohols, the rise velocity reached maximum at 5-50mm distance from the
orifice. But, for distilled water and high concentration of alcohols no maximum
velocities were observed. Finally, the local bubble velocity was analyzed as a

33
function of the adsorption coverage of surfactant on the bubble surface.

Figure 2 11: a. Velocity profiles for 2.2mm bubbles in MIBC, b. Terminal velocity vs. bubble size
in the presence of some frothers (Sam, 1995).

34
Azgomi et al. (2007), trying to characterize frothers, reported that for the same
gas holdup and gas rate, the bubble size depended markedly on frother type
(Figure 2.12). This observation gave rise to the hypothesis explored in this thesis
namely that frother type can affect bubble rise velocity.

Figure 2.12: Bubble size measurement at same gas holdup (8%) for F150 and
Pentanol (Azgomi et al., 2007).

As a first investigation of the hypothesis Acuna (2008) studied the impact of

frother type on the rise velocity in a multi-bubble system. The results proved that
frother type can have a significant effect on bubble rise velocity. Figure 2.13
shows the effect of F150 and pentanol on the velocity of bubbles in the swarm.
According to Figure 2.13 F150 significantly reduced the velocity compared to
pentanol, which acted similar to clean water. This result agrees with the
conclusion of Azgomi et al. (2007).

35
 Figure 2.13: Comparison between influences of F150 and Pentanol on terminal
rise velocity of bubbles in swarms (Acuna, 2008).

2.4.3. Salts
Some salts produce small bubbles and in that sense act like frothers (Quinn et
al., 2007). Like surfactant salts can create surface tension gradients and set up
Marangoni effect stresses. As a consequence mobility of the interface is altered
and an effect on bubble rise velocity can be expected. But, the electrolyte effect
is much smaller (i.e., high concentrations are required (Quinn et al., 2007)) than
is the case for surfactant (Henry et al., 2008).

The effect of electrolyte remains unclear. Craig et al. (1993), Rebeiro and Mewes
(2007), and Henry et al. (2008) reported that some salts inhibit coalescence and
others do not. Lee and Hodgson (1968) suggested that electrolytes give rise to
dynamic increases in interfacial tension and thus retard the surface flow of thin
liquid films, leading to an immobile or a partially mobile interface.

Finch et al. (2008) suggested a possible explanation for the action of salts in
forming small bubbles that was based on two assumptions: i) a high
concentration of salt is needed; ii) salt should increase surface tension. Figure

36
2.14 describes the air/water interface under these conditions. Here the water
molecules provide the low surface tension site (compared to salt molecules) and
force is generated away from this point. Therefore an opposing force is
generated like in the action of surfactant. Here water molecules have taken on
the role of surfactant.

Figure 2.14: Suggested explanation for action of high concentration salts which
act like frother (Finch et al. 2008).

Detsch and Harris (1989) studied the dissolution and rise velocity of small air
bubbles in water and salt water. The results indicated that the bubble velocity in
the presence of salt was lower than in pure water.

Figure 2.15: Influence of potassium chloride concentration on terminal rise

velocity (Jamialahmadi and Muller-Steinhagen,1992).

Jamialahmadi and Muller-Steinhagen (1992) studied the effect of ethanol and

potassium chloride concentration on bubble rise velocity in swarms. Figure 2.15

37
shows the dependency of bubble size and rise velocity on reagent concentration.
Adding of trace amount of potassium chloride reduced the terminal rise velocity
compared to pure water. However, after increasing salt concentration no frother
significant reduction was achieved. The authors suggested that the ionic forces
formed in the bulk of the solution reduced the terminal rise velocity and reinforce
the resistance of the liquid film on the bubbles against coalescence. As a
consequence the bubble size increase seems to be in contradiction.
Kugou et al. (2003) studied the motion of air bubbles in seawater. They reported
that for small bubble size (<3mm) the rise velocity was almost the same as in
artificial seawater and lower than that in distilled water. However, for larger
bubbles (>3mm) the velocity in seawater was almost the same as in distilled
water.

Quinn et al. (2007) compared the influence of some salts with MIBC (as an
example frother). The results indicated that there was a correlation between gas
holdup and ionic strength of salts. Gas hold up for a salt solution with ionic
strength of 0.4-0.5, was similar to that of 7-10ppm MIBC, which is a typical
industrial dosage for this common frother.

Henry et al. (2008) measured the terminal rise velocity of small bubbles
(de<100μm, Re<1) in some electrolyte solutions. The results indicated that
terminal rise velocity was in good agreement with the Hadamard-Rybczynski
model (mobile surface as in pure water). In addition, there was no significant
difference in the velocity between electrolytes that inhibit bubble coalescence,
and others that have no influence.

In summary, all observations confirm the influence of high concentration of some

salts on preventing coalescence and producing small bubbles. But in the case of
an influence of salts on bubble rise velocity, there is no uniformity among
investigators.

38
CHAPTER THREE: EXPERIMENTAL SETUP
The methods for measurement of bubble rise velocity can be classified as either
intrusive or non-intrusive. A non-intrusive measurement method is desirable and
photography is considered the most practical (Kulkarani and Joshi, 2005).
Chapter three describes the photographic technique used.

3.1. Equipment

3.1.1. Column setup

A circular Plexiglas column 6.35cm diameter by 350cm high was used
surrounded by a square Plexiglas water jacket (8 x 8 x 330 cm) (Figure 3.1). A
measuring tape was placed along the central axis of the column to measure the
size and local velocity of the bubbles. The column diameter was large enough to
avoid wall effects for bubbles < 3 mm (Grace, 1973; Narayanan et al., 1974;
Bhaga, 1976; Clift et al., 1978). To control a uniform temperature along the
column water was circulated through the jacket; the square column also avoided
optical distortion associated with a curved surface.

3.1.2. Air line

Air was provided from a controllable compressed air system with flow rate
adjusted by an online monitoring system. Plastic tubes and connectors were
used to transfer air from the source to the glass capillary at the bottom of the
column. The air was from the university compressor and was dry.

3.1.3. Camera moving device

A mobile digital video camera was used to track a single bubble during its rise.
To follow the bubble it is necessary to have a variable speed motor, in this case
driving a chain belt over a pulley (Figure 3.1). Limit switches were placed at the
bottom and top of the column to arrest the movement. The movement of the
camera was controlled manually through the variable speed controller over a
range from zero to 50 cm/s, the experimenter adjusting the speed to keep the
bubble in view (on a monitor) during its rise.

39
A high resolution CCD digital video camera recorder (Canon GL2), a monitor
(Sony PVM-1340) and a signal sender set (Radio Shack 15-2572) were used.
The video camera recorded 30 frames per second. When used to obtain the
shape and size of the bubble, a shutter speed 1/1000 of a second was set.

Figure 3.1: The experimental column setup.

3.1.4. Capillaries
In this work three glass capillaries were used with 25, 51 and 75mm inside
diameter, manufactured by Friedrich & Dimmock.

40
3.2. Requirements

3.2.1. Temperature control

Any temperature variation along the column would affect bubble motion;
consequently the temperature was kept uniform at room temperature by
circulating water. To achieve room temperature, Montreal tap water was held in a
large container (55 L, sufficient for both preparation of test solution as well as
circulating water) for over 10 hours prior to a test. The temperature remained in
the range 24 to 26˚C.

3.2.2. Bubbling frequency

Bubble frequency up to 80 bubbles per minute has been shown to have no effect
on velocity (Sam et al., 1996). As a consequence, bubble frequency was
adjusted to less than 80 per minute for all current tests.

3.2.3. Water saturation

It was suspected that the humidity of the air might affect the bubble rise velocity.
Zhang (2000) reported no obvious difference between “dry” and “water-
saturated” bubbles in either tap water or contaminated water. Based on this no
special precautions regarding humidity were taken.

3.3. Procedures

3.3.1. Bubble velocity profile

To set up, the column was filled with tap water and appropriate concentration of
reagent. Tap water was circulated inside the water-jacket layer to keep the
temperature uniform at room temperature. Single bubbles were generated at a
stable frequency regime (less than 80 bubbles per minute). The experiment was
initiated by activating the mobile video camera at the moment a bubble was
released from the orifice. The images captured by the tracking camera were
displayed on a monitor and the experimenter adjusted the speed to maintain the
single bubble at approximately the center of the field of view. Images were

41
recorded on digital tape and were later transferred to a computer for data
processing.

3.3.2. Data Processing

To process the data several steps were executed (Figure 3.2). The captured
images contained the data required to determine velocity profile and bubble size
(and to check frequency). The information was transferred from digital tape to a
computer using Windows Movie Maker software and was converted to a video
file. The video file was cut into parts using the software and put in different
folders according to the type of information sought. The video files were
processed to measure bubble size and obtain velocity profile and terminal
velocity.

All results were entered into a database. The results were checked and if errors
(such as low level of reliability, abnormal data, etc.) were detected the
measurement was repeated. The database was developed using Microsoft Excel
and consisted of four layers: data entry, data summary, calculations and results.

42
 Provide Experiment Run Experiment
Requirements

Measure Capture Get Bubble

Operational Factors Velocity Profile Size Data

Convert To
Video

Convert To
Image
Checking

Prepare Measure Measure

Repeat Velocity Profile Terminal Velocity Bubble Size
Final
Result
Database

Figure 3.2: The data processing flowchart.

3.4. Reagents

Ten reagents were tested consisting of a homologous series of aliphatic

alcohols, three isomers of hexanol, including MIBC, two polyglycols and
salt (NaCl). Table 3.1 gives some properties of the reagents.

43
 Table 3.1: Summary of reagents types and properties.
Molecula
Reagent Structure Formula r Weight Supplier
g/gmol
CH3CH2CH2CH2
Aliphatic alcohol Sigma
1-Butanol 74
Aldrich
OH

CH3CH2CH2CH2CH2
Sigma
1-Pentanol Aliphatic alcohol OH 88.15
Aldrich

MIBC CH3CHCH2CHCH3
Sigma
(Methyl Iso Butyl Aliphatic alcohol CH3 OH 102.18
Aldrich
Carbonil)

CH3CH2CH2CH2CH2CH2
Sigma
1-Hexanol Aliphatic alcohol OH 102.18
Aldrich

CH3CH2CH2 CH2 CH2CH2

Sigma
2-Hexanol Aliphatic alcohol 102.18
Aldrich
OH

CH3CH2CH2CH2CH2CH2CH2
Sigma
1-Heptanol Aliphatic alcohol OH 116.20
Aldrich

CH3CH2CH2CH2CH2CH2CH2CH2
Sigma
1-Octanol Aliphatic alcohol OH 130.22
Aldrich

Dow
chemical
Dowfroth 250 Polyglycol ether CH3(C3H6O) 4OH 264.35
company,
USA
Sodium Chloride Salt NaCl 206.29 Flottec, USA

F150 Polyglycol H(C3H6O)7OH 425 Flottec, USA

44
3.5. Measurement techniques

3.5.1. Bubble position

To measure bubble rise distance (from zero, the capillary tip) the technique
illustrated in Figure 3.3 was used. The position of the bubble centre, the height of
the lower line and the distance between upper and lower lines were measured in
pixels using Adobe Photoshop software. Since the distance between the upper
and lower lines is 4 mm, the height of bubble center was calculated from the
following equation:

HB(mm)= HL(mm) + 4 x ((HB(Pix) – HL(Pix)) / ((HU(Pix) – HL(Pix))) (3.1)

where HB, HL and HU are height of bubble, upper line and lower line,
respectively.

Figure 3.3: The required information for measuring bubble height during rise on one image.

3.5.2. Local velocity

Figure 3.4 shows the technique for measuring local rise velocity (Ub). Here the
local velocity was considered as the average velocity of a bubble over time
interval of t1 to t2. By measuring the corresponding distance traveled by the
bubble (from H1 to H2) the local velocity was calculated using the following
equation:

45
 H 2 − H1
Ub = (3.2)
t 2 − t1

As change in velocity is initially rapid as bubbles accelerate from zero velocity,

over the first second, the Δt= t2 – t1 was short, 66ms; for times>1s Δt was larger,
1000ms. The velocity profile was plotted against the mid point of the interval, i.e.,
in space at H= (H1+H2)/2 or in time at t= (t1+t2)/2.

3.5.3. Bubble size

To measure bubble size the technique shown in Figure 3.5 was applied. A
camera was put at “front” and “side” positions relative to the column. High
resolution images were taken in each position recorded on digital tape. The
images were extracted from the video files using Frame Shot software. The size
of bubble in each image was measured using Adobe Photoshop or Able Image
Analysis software.

Figure 3.4: The applied technique for measuring local velocity.

46
 Figure 3.5: The technique applied for measuring bubble size.

3.5.4. Reagents and choice of reagent concentration

To compare the influence of reagent type on bubble rise velocity, a choice of
concentration range is required. Given a prime use of frother is control of bubble
size, the choice of reagent concentration was based on that criterion.

Same bubble size line

Figure 3.6: The description of technique that applied to determine equivalent concentrations of
F150 and 1-Pentanol (adapted from Finch et al. 2008).

47
An example will serve to show the approach. Finch et al.(2008) reported the
influence of type and concentration of some frothers on bubble size. Figure 3.6
presents the influence of concentration on bubble size for F150 and pentanol. A
horizontal line is shown at 2mm bubble size which links the concentration for the
two frothers. From this result, 2ppm of F150 is equivalent to 9ppm 1-pentanol.
Table 3.2 presents the equivalent concentrations (listed 1-6) for the reagents
based on this approach and applied in this work.

Table 3.2: The equivalent concentrations of applied reagents.

Equivalent Concentration
Reagent type
1 2 3 4 5 6
1-Butanol (ppm) 11.5 25 41 58 82 246
1-Pentanol (ppm) 7 15 25 35 50 150
1-Hexanol (ppm) 5.25 11.3 18.5 26.2 37.5 112.5
2-Hexanol Alcohol 5.25 11.3 18.5 26.2 37.5 112.5
1-Heptanol (ppm) 4.5 9.6 16.5 22.5 32 96
1-Octanol (ppm) 4.5 9.5 16 22.3 32 96
MIBC (ppm) 2.5 5 7.5 10 20 60
Dowfroth 250 (ppm) 3 6 10 15 25 75
Polyglycol
F150 (ppm) 1 2 3 5 10 30
Sodium Chloride (mol/L) Salt 0.1 0.2 0.3 0.4 1 3

Six equivalent concentrations (1-6) were selected to compare reagents.

Equivalent concentration 6 represents three times equivalent concentration 5 to
include a “very high” concentration.

48
CHAPTER FOUR: RESULTS AND DISCUSSION

4.1. Reliability

4.1.1. Bubble generation

The three glass capillaries generated bubbles in three size classes. Table 4.1
shows the range of bubble frequency achieved for each capillary. The frequency
of generated bubbles depends on inside diameter and length of capillary. The
frequency is a function of the minimum gas rate required for generating a bubble,
the water level in the column and air chamber volume. Generally, smaller inside
diameter and longer capillaries help the system to work stably at low frequency.

Table 4.1: The range of bubble size and frequency.

Bubble Size Bubble Frequency
(mm) (bubble/min)
0.70-0.97 14-26
1.50-1.60 47-55
1.91-2.00 70-80

All experiments for a given capillary were executed at the same gas flow rate.
Figure 4.1 presents the variation of single bubble size vs. frequency produced
with the 25μm capillary.

According to Figure 4.1 bubble size was reduced by an increase in frequency, as

expected, for a given flowrate. The trend appears independent of reagent type.
Figure 4.2 shows the same trend is observed for all three capillaries. The two
larger two capillaries gave tighter control over the bubble size. Figure 4.3
presents bubble diameter vs. equivalent concentration for some of the reagents.
There is a slight but persistent difference in bubble size between frother types.

49
 1.1

1.0

0.9
Bubble Size (mm)

0.8

0.7

0.6
1-Butanol 1-Pentanol

0.5 1-Hexanol 1-Heptanol

1-Octanol MIBC
0.4 DF250 F150
NaCl
0.3
15 20 25 30 35 40
Bubble Frequency (bubble/min)

Figure 4.1: Variation of single bubble size vs. bubble frequency for reagents using 25μm capillary.

2.5

2
Bubble Diameter (mm)

1.5

1
Capillary 25μm
Capillary 51μm
Capillary 75μm
0.5
Linear (Capillary 25μm)
Linear (Capillary 51μm)
Linear (Capillary 75μm)
0
0 20 40 60 80 100
Bubble Frequency (bubble/min)

Figure 4.2: The variation of single bubble size vs. bubble

frequency for the three applied capillaries.

50
 1

0.9

0.8

0.7
Bubble Diameter (mm)

0.6

0.5 1-Pentanol
1-Heptanol
0.4
1-Octanol
MIBC
0.3
Linear (1-Pentanol)
0.2 Linear (1-Octanol)
Linear (1-Octanol)
0.1 Linear (MIBC)

0
0 1 2 3 4 5 6 7
Equivalent Concentration

Figure 4.3: Bubble size as a function of equivalent concentration for 25μm capillary.

4.1.2. Terminal velocity

To measure terminal velocity first it is necessary to construct the velocity

profile to be sure that the bubble reaches the constant terminal velocity
stage (according to Figure 1.1). Figure 4.4 shows a velocity profile of a
single bubble (1.45mm) rising in F150 solution, which exhibits the
characteristic profile and shows that the bubble does reach terminal
velocity in this case. In the Figure the main clue that terminal velocity is
reached is the gradual increase in the “constant” velocity due to gradual
increase in bubble size during rise. As a result if the velocity profile exhibits
this characteristic the velocity could be considered as terminal velocity. If
the profile is still showing a decreasing trend the rise velocity at that a
given point is sometimes called “apparent terminal velocity” in order to
compare with literature data.

51
 30

Local Velocity (cm/s) 25

20

15

10

5
F150 1ppm

Constant Velocity Line

0
-250 0 250 500 750 1000 1250 1500 1750 2000 2250 2500 2750 3000 3250 3500
Distance (mm)

Figure 4.4: An example of velocity profile where bubble reaches terminal velocity
in F150 1ppm for ca. 1.45mm bubble.

In each experiment the profiles of at least three bubbles were recorded. An

estimate of measurement error is given in Figure 4.5. The term H(mm) in
the table in Figure 4.5 refers to the mid height over the last 1.6 ms. The
size of bubble corresponding to that height was calculated from the
measured value at zero height by knowing the hydrostatic pressure.

If there was no obvious difference among measured rise velocities, the

average velocity along the profile was taken. If the data did not check, the
experiment was repeated.

52
 Figure 4.5: An example of measuring terminal rise velocity and reliability.

4.1.3. Bubble size

To record bubble size the camera was put at “front” and “side” positions relative
to the column (Figure 3.5). By combining the measured bubble size in two
positions an estimate of error could be obtained by comparing the two
measurements in the Z-direction.

Table 4.2 is an example of the size measurement calculations. Results of six

images were taken to give the size of bubble with acceptable precision. The
bubble size was measured essentially at the capillary tip; to give bubble size at
the top of the column the ideal gas law was applied, knowing the pressure (water
depth). As there are slight differences between bubble sizes for a given orifice as
frother type is changed reference is made to, for example, ca. 1.5mm diameter.
Where the range is typically less than ±0.05mm.

53
 Table 4.2: An example of measuring bubble size and calculating measurement error.
Direct Measurement of Bubble Size
Front View-Pixels
# X Z Scale Code
1 23 22 97 1
2 23 22 97 1
3 23 22 98 1
4 22 21 98 1
Average 22.75 21.75 4
SD 0.50 0.50
Error(%) 2.20 2.30
Side View-Pixels
# Y Z Scale Code
1 31 31 131 1
2 31 30 130 1
3 32 31 131 1
4 0
Average 31.33 30.67 3
SD 0.58 0.58
Error(%) 1.84 1.88
Bubble Size After Scaling (mm)
# X Z Y Z
1 0.71 0.68 0.71 0.71
2 0.71 0.68 0.72 0.69
3 0.70 0.67 0.73 0.71
4 0.67 0.64 0.00 0.00
Average 0.70 0.67 0.72 0.70
SD 0.02 0.02 0.01 0.01

4.2. Velocity profile analysis

4.2.1. Examples
In this section some velocity profiles obtained in this work are compared with the
typical profiles described in Figure 1.1. Figure 4.6 shows the velocity profile for
four concentrations of F150. The profiles exhibit the typical features and trends.
Figure 4.7 expands the first 500mm of the profiles magnify the first and second
stages.

54
 40

35

30
Local Rise Velocity (cm/s)

25

20

15

10 1ppm
3ppm
5
5ppm
10
0
-200 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Distance (mm)
Figure 4.6: Velocity profiles in F150 (ca 1.5mm).

40

35

30
Local Rise Velocity (cm/s)

25

20

15

10 1ppm
3ppm
5
5ppm
10
0
-50 0 50 100 150 200 250 300 350 400 450 500
Distance (mm)

Figure 4.7. Velocity profiles in F150 (ca 1.5mm) over the first 3 seconds for
conditions in Figure 4.6.

55
According to Figure 4.7, as concentration is increased the bubble reaches
terminal velocity faster, which is in agreement with observations of Sam et al.
(1996) and Zhang and Finch (2000).

4.2.2. Maximum velocity

It has been reported that the higher the concentration of reagent the lower the
maximum velocity attained on the profile, suggestive of faster mass transfer of
reagent molecules to the bubble surface (Sam et al., 1996). Figure 4.8 presents
the influence of concentration on maximum velocity in the presence of MIBC,
NaCl and F150. According to Figure 4.8 the higher concentration of MIBC and
F150 strongly reduced the maximum velocity. However, addition of NaCl
concentration did not change the maximum velocity as significantly.

40

35
Maximum Rise Velocity (cm/s)

30

25

20

15

10
F150
5 MIBC
NaCl
0
0 1 2 3 4 5 6 7
Equivallent Concentration
Figure 4.8: The influence of reagent concentration on maximum velocity
in the presence of MIBC, NaCl and F150.

4.3. Reagent type: pentanol vs. F150

Azgomi et al. (2007) reported that for the same gas holdup and gas rate, bubble
size nevertheless depended on frother type, the extreme case being between

56
1-pentanol and F150 (Figure 2.12). This observation gave rise to the hypothesis
that frother type can affect the bubble rise velocity of same size bubbles. While
hinted at in the prior works of Zhou et al. (1992), Sam (1995) and Zhang (2000)
the differences were small and could have been ascribed to experimental error.

To test the hypothesis Acuna and Finch (2008) compared 1-pentanol and F150
by measuring the rise velocity of individual bubbles in a multi-bubble system
(Figure 2.13). The results established that F150 significantly reduced the rise
velocity compared to 1-pentanol. Indeed 1-pentanol acted very similar to pure
water.

Azgomi et al. speculated that bubble charging may be a factor, a sedimentation

potential effect controlling rise velocity. Elmahdy et al. (2008) measured the zeta
potential of air bubbles in the presence of F150 and 1-pentanol showing only
minor differences and concluded bubble changing was not a factor. This leaves
unknown bubble interactions to explain the results of Azgomi et al. and Acuna
and Finch or a difference in single bubble velocity.

In this work the rise velocity of single bubbles was measured in the presence of
F150 and 1-pentanol for a bubble size range of 0.8 to 2mm.

4.3.1. Velocity profile

Figure 4.9 presents the velocity profiles (velocity vs. distance) for ca. 1.45mm
bubbles in F150, pentanol and tap water, including some full repeats that confirm
the reliability. Figure 4.9 clearly reveals that the reagent type affected the velocity
in the concentration range tested (which is of interest in flotation). In the
presence of F150 the bubble rapidly reached terminal velocity while in 1-
pentanol, the bubble velocity was much higher, similar to water and apparently
still decreasing to approach terminal.

57
 40

35

Tap Water
30
Local Rise Velocity (cm/s)

1-Pen 7ppm-Test 1
25
1-Pen 7ppm-Test 2

20
1-Pen 50ppm

15 F150 1ppm-Test 1

10 F150 1ppm-Test 2

F150 10ppm
5

0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.9: Velocity profiles in F150, 1-pentanol and tap water (ca 1.45mm).

4.3.2. Comparison of terminal/apparent terminal velocities

In the case of F150, Figure 4.9 shows terminal velocity is reached – the
characteristic increasing “constant” velocity stage is evident. In the case of 1-
pentanol, however, Figure 4.9 shows the velocity is only the apparent terminal.
Figure 4.10 presents terminal / apparent terminal rise velocity vs. bubble
diameter in the presence of F150, 1-pentanol and tap water, compared with
results of Acuna and Finch (2008) and the results for clean and contaminated
water given by Clift et al. (1978). As Acuna and Finch (2008) measured the rise
velocity at 500mm, the apparent terminal velocities at this distance were
determined to make comparison with their work. The presence of F150 shows a
significantly lower terminal velocity compared to either tap water or 1-pentanol. In
both swarms and single bubble systems, the presence of 1-pentanol hardly
influences the rise velocity relative to clean water, while the results of F150
approach contaminated water.

58
 40

35
Apparent Terminal Rise Velocity (cm/s)

30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bubble Diameter (mm)
F150-Current Work@3000mm 1-Pentanol-Current Work@3000mm
F150-Current Work@500mm 1-Pentanol-Current Work@500mm
F150-Acuna and Finch@500mm 1-Pentanol-Acuna and Finch@500mm
Contaminated Water (Clift et al., 1978) Clean Water (Clift et al., 1978)

Figure 4.10: The terminal/apparent terminal rise velocity vs. bubble diameter at 500 and 3000mm
distance in the presence of F150 and 1-Pentanol compared to swarms results (Acuna and Finch,
2008) and results for single bubble in clean and contaminated water given by Clift et al. (1978).

Regarding Figure 4.9 and Figure 4.10 there is a clear difference between rise
velocity in F150 and 1-pentanol. As a consequence, the observation of Azgomi et
al. has its origin in the velocity of single bubbles.

4.4. Aliphatic alcohols

As a start to understand the surfactant structure / bubble velocity relationship a
homologous series of five aliphatic n-alcohols (C4-C8) was used to investigate the
influence of chain length.

59
Figure 4.11 and Figure 4.12 show the terminal/apparent terminal rise velocity vs.
bubble diameter at 3000mm for equivalent concentrations 1 and 5, of 1-pentanol,
1-hexanol and 1-heptanol (Figure 4.11); and 1-butanol, 1-hexanol and 1-octanol
(Figure 4.12). The Figures indicate that the lower concentration of 1-hexanol
(equivalent concentration 1=5.25ppm) acted like 1-butanol and 1-pentanol, and
the higher concentration (equivalent concentration 2 =37.5ppm) acted like 1-
heptanol and 1-octanol. For 1-butanol, 1-pentanol, 1-heptanol and 1-octanol, the
change in concentration did not influence rise velocity practically.

To check if the terminal velocity was achieved, the velocity profiles were
examined. Figure 4.13 compares the profiles in 5.25ppm and 37.5ppm 1-
hexanol. The 5.25ppm velocity profile has probably not reached terminal velocity
because there is a discernable decreasing trend, while the profile at 37.5 ppm
has reached terminal velocity.

40
Apparent Terminal Rise Velocity (cm/s)

35

30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bublble Diameter (mm)
1-Pentanol 1-Pentanol
1-Hexanol 1-Hexanol
1-Heptanol 1-Heptanol
Contaminated Water (Clift et al., 1978) Clean Water (Clift et al., 1978)

Figure 4.11: The terminal/apparent terminal rise velocity vs. bubble diameter at
3000mm in the presence of low (1) and high (5) concentrations of 1-pentanol, 1-
hexanol and 1-heptanol.

60
 40

35

Aparent Terminal Rise Velocity (cm/s)

30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bublble Diameter (mm)
1-Butanol 1-Butano
1-Hexanol 1-Hexanol
1-Octanol 1-Octanol
Contaminated Water (Clift et al., 1978) Clean Water (Clift et al., 1978)

Figure 4.12: The terminal/apparent terminal rise velocity vs. bubble diameter at 3000mm in the
presence of low (1) and high (5) concentrations of 1-butanol, 1-hexanol and 1-octanol.

40

35

30
Local Rise Velocity (cm/s)

25

20

15

10

5 1-Hexanol 5.25ppm
1-Hexanol 37.5ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Bubble Position (mm)

Figure 4.13: Velocity profiles in 1-hexanol (ca 1.5mm).

61
4.4.1. Concentration effect
Figure 4.11 and 4.12 indicate that 1-pentanol and 1-butanol have not reached
terminal velocity even at the highest concentration tested (5) while, the 1-
heptanol and 1-octanol have. 1-Hexanol is in between: at high concentration (5) it
acts like 1-heptanol and at low concentration (1) it acts like 1-pentanol. The
implication is that if we go to higher concentrations of 1-pentanol than tested thus
far it too will start to look like 1-heptanol; conversely, 1-heptanol at lower
concentrations than tested will take on the character of 1-pentanol. The jump in
apparent terminal velocity from 1-pentanol to 1-heptanol is then a ”concentration
effect”.

45

40

35
Local Rise Velocity (cm/s)

30

25

20

15
Tap Water
1-Butanol-11.5ppm
10 1-Butanol-82ppm
1-Butanol-125ppm
5 1-Butanol-150ppm
1-Butanol-180ppm
1-Butanol-260ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.14: Velocity profiles in 1-butanol (ca 1.45mm).

62
 40

35

30
Local Rise Velocity (cm/s)

25

20

15
Tap Water
10 1-Pentanol-7ppm
1-Pentanol-50ppm
1-Pentanol-110ppm
5
1-Pentanol-130ppm
1-Pentanol-250ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.15: Velocity profiles in 1-pentanol (ca 1.45mm).

40

35

30
Local Rise Velocity (cm/s)

25

20

15

Tap Water
10 1-Pentanol-7ppm
1-Pentanol-50ppm
1-Pentanol-110ppm
5 1-Pentanol-130ppm
1-Pentanol-225ppm
1-Pentanol-275ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.16: Velocity profiles in 1-pentanol (ca 1.85mm).

63
 45

40

35
Local Rise Velocity (cm/s)

30

25

20

15

10 Tap Water
1-Hexanol-5.25ppm
5
1-Hexanol-15ppm
1-Hexanol-25ppm
1-Hexanol-37.5ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)
Figure 4.17: Velocity profiles in 1-hexanol (ca 1.45mm).

This concentration effect was explored up. Figure 4.14 show the case of 1-
butanol; Figure 4.15 and Figure 4.16 show the velocity profile in 1-pentanol for
1.45mm and 1.85mm bubble sizes, respectively; and Figure 4.17 and Figure 4.18
indicates the velocity profile in 1-hexanol for 1.45mm and 1.85mm bubbles,
respectively. According to the velocity profiles for these three n-alcohols, as the
concentration increased, the rise velocity reduced to a value close to the
contaminated water result, except in the case of 1-butanol even at 260ppm.

64
 40

35

30
Local Rise Velocity (cm/s)

25

20

15

Tap Water
10
1-Hexanol-5.25ppm
1-Hexanol-15ppm
5
1-Hexanol-25ppm
1-Hexanol-37.5ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.18: Velocity profiles in hexanol (ca 1.85mm).

Krzan and co-workers report velocity profiles for 1-butanol and 1-hexanol (Krzan
and Malysa, 2002) and 1-pentanol and 1-octanol (Krzan et al., 2007). They
obtained the profiles over the more limited distance of 350mm.

Taking results at 350mm as “apparent” terminal velocity in this case, Figure 4.19,
Figure 4.20 and Figure 4.21 compare the results with those of Krzan and co-
workers. The figures indicate that the results of the current work at 350mm are
close to those of Krzan and co-workers.

65
 40

35
Apparent Terminal Velocity (cm/s)
30

25

20

15

10

5 Current Work-1.45mm@350mm

Krzan et al-1.42mm@350mm
0
0 500 1000 1500 2000 2500 3000
1-Butanol Concentration (ppm)

Figure 4.19: Apparent terminal velocity (at 350mm) vs. concentration of single bubbles in 1-
butanol.

40

35
Apparent Terminal Velocity (cm/s)

30

25

20

15

10

Current Work-1.45mm@350mm
5
Krzan et al-1.42mm@350mm
0
0 50 100 150 200 250 300
1-Pentanol Concentration (ppm)

Figure 4.20: Apparent terminal velocity (at 350mm) vs. concentration of single bubbles in 1-
pentanol.

66
 35

Apparent Terminal Velocity (cm/s) 30

25

20

15

10

5 Current Work-1.45mm@350mm

Krzan et al-1.42mm@350mm
0
0 10 20 30 40 50 60 70 80
1-Hexanol Concentration (ppm)

Figure 4.21: Apparent terminal velocity (at 350mm) vs. concentration of single bubbles in 1-
hexanol.

35

30
Apparent Terminal Velocity (cm/s)

25

20

15

1-Butanol
10
1-Pentanol
1-Hexanol
5 1-Heptanol
1-Octanol
Water Only
0
0.01 0.1 1 10 100 1000
Concentration (ppm)

Figure 4.22: Apparent terminal velocity (at 3000mm) vs. concentration (ppm) of single bubbles for
series of n-alcohols for ca. 1.45mm bubbles.

67
 35

30
Apparent Terminal Velocity (cm/s)

25

20

15

1-Butanol
10
1-Pentanol
1-Hexanol
5 1-Heptanol
1-Octanol
Water Only
0
0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1
Concentration (mol/L)

Figure 4.23: Apparent terminal velocity (at 3000mm) vs. concentration (mol/L) of single bubbles
for series of n-alcohols for ca. 1.45mm bubbles.

35

30
Apparent Terminal Velocity (cm/s)

25

20

15

10 1-Pentanol-1.45mm

1-Hexanol-1.45mm
5 1-Pentanol-1.85mm

1-Hexanol-1.85mm
0
1 10 100 1000
Concentration (ppm)
Figure 4.24: Apparent terminal velocity (at 3000mm) vs. concentration (ppm) for ca. 1.45 and
1.85mm single bubbles in 1-pentanol and 1-hexanol.

68
Figure 4.22 and Figure 4.23 show the apparent terminal velocity at 3000mm vs.
concentration based on ppm and mol/L, respectively, for the n-alcohols used in
this study. To explore the influence of bubble size on concentration effect, Figure
4.24 presents the apparent terminal velocity at 3000mm vs. concentration for ca.
1.45 and 1.85mm single bubbles in 1-pentanol and 1-hexanol.

There are several observations compared with Figure 4.20- 4.25. First, there is a
critical concentration (CC) to reach terminal velocity that decreases as the chain
length increases (Figure 4.23). Second, traveling distance of bubble influences
the estimate of terminal velocity. For instance, the apparent terminal velocity at
350mm (Figure 4.20-4.22) is higher than at 3000mm (Figure 4.23), consequently
the results of Krzan and co-workers do not represent true terminal velocity,
especially for low concentrations. Third, comparison of apparent terminal velocity
for 1.45 and 1.85mm bubbles (Figure 4.25) indicates that the larger bubble size
requires a higher critical concentration to reach terminal velocity; for instance, in
1-pentanol the critical concentration for 1.45mm bubble is about 130ppm while
for 1.85mm it is about 250ppm. Fourth, at concentrations above the critical
concentration the terminal rise velocity of all examined alcohols are close i.e.,
frother type did not influence terminal velocity.

4.4.2. The influence of molecular structure: C-6 alcohols

To expand the observations on 1-hexanol, two isomers, 2-hexanol and MIBC,
were included. The difference between the isomers is location of the OH and CH3
groups. The OH group is bonded with an end CH2 group in 1-hexanol and with
the second to last CH group in 2-hexanol. In MIBC the OH group is also bonded
with the CH group but it has three CH3 groups.

Figure 4.25 presents the terminal/apparent terminal rise velocity vs. bubble
diameter in the presence of two concentrations (equivalents 1 and 5) of 1-
hexanol, 2-hexanol and MIBC; as with the 1-hexanol a difference between low

69
and high concentration is observed for 2-hexanol, although the difference is less.
For MIBC there is no obvious difference between equivalent concentration 1 and
5.

Figure 4.26 shows the velocity profiles for 5.25 and 37.5ppm of 2-hexanol. Like
the 1-hexanol profiles, the bubble did not reach terminal velocity at the low
concentration. Figure 4.27 presents the apparent terminal velocity vs.
concentration in the presence of 1-hexanol, 2-hexanol and MIBC. Here MIBC
reaches terminal velocity at very low concentration compared to the other two
isomers; Sam et al. (1996) also found MIBC gave terminal velocity at low dosage
(1ppm).

40

35
Apparent Terminal Rise Velocity (cm/s)

30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bubble Diameter (mm)

1-Hexanol-Equiv. Conc. 1 1-Hexanol-Equiv. Conc. 5

2-Hexanol-Equiv. Conc. 1 2-Hexanol-Equiv. Conc. 5
MIBC-Equiv. Conc. 1 MIBC-Equiv. Conc. 5
Contaminated Water (Clift et al., 1978) Clean Water (Clift et al., 1978)

Figure 4.25: The terminal/apparent terminal rise velocity vs. bubble diameter at 3000mm in the
presence of MIBC, 1-hexanol and 2-hexanol.

70
 35

30

25
Local Rise Velocity (cm/s)

20

15

10
2-Hexanol-5.25ppm

5
2-Hexanol-37.5ppm
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.26: Velocity profiles in 2-hexanol (ca 1.5mm).

35

30
Apparent Terminal Velocity (cm/s)

25

20

15

10 1-Hexanol

2-Hexanol
5
MIBC

0
0.01 0.1 1 10 100
Concentration (ppm)

Figure 4.27: Apparent terminal velocity vs. concentration of single bubbles in 1-

hexanol, 2-hexanol and MIBC.

71
According to Figures 4.25-4.27 the chemical structure of the alcohol influences
the rise velocity of single bubbles. According to the molecular structure properties
of the isomers the order of decreasing hydrophilic character is MIBC>2-
hexanol>1-hexanol which corresponds to their order of terminal velocity. The
same order was seen in solubility, for instance the solubility of MIBC and 1-
hexanol is the maximum and minimum among them that is 17 and 6g/L,
respectively.

So the solubility difference between 1-hexanol and MIBC is not enough big
(compared to the solubility difference between other alcohols) to support the
observed significant difference in bubble rise velocity. The hydrophilicity could be
determined using “Hydrophil-Lipophil Balance (HLB)” (Rao, 2004), however the
calculated HLB for MIBC and 1-hexanol are 6.1 and 6, respectively, that does not
reflects significant difference too.

It seems that the structure affects the orientation of frother molecule on the
bubble surface. Perhaps the orientation of MIBC molecules has some advantage
compared to 1-hexanol and 2-hexanol, which permits the lower concentration
control over bubble surface drag or surface viscosity.

4.4. Comparison of MIBC and NaCl

Quinn et al. (2007) compared the influence on gas holdup and bubble size of
some salts with MIBC (as a typical frother). The results indicated that a salt
solution with ionic strength of 0.4-0.5, acted similarly to that of 7-10ppm MIBC.

In this work the rise velocity of single bubbles in the presence of MIBC and NaCl
was measured to explore this reported similarity. Figure 4.28 presents the
velocity profiles in the presence of MIBC and NaCl that shows MIBC reached
terminal velocity, while NaCl may be still in the deceleration region.

72
 40

35

30
Local Rise Velocity (cm/s)

25

20

15

10 MIBC-Equiv. Conc. 1
MIBC-Equiv. Conc. 5
5 NaCl-Equiv. Conc. 1
NaCl-Equiv. Conc. 5
0
-300 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300
Distance (mm)

Figure 4.28: Velocity profiles in MIBC (ca. 1.5mm) and NaCl (ca 1.6mm).

40

35
Apparent Terminal Rise Velocity (cm/s)

30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bubble Diameter (mm)
MIBC NaCl
Contaminated Water (Clift et al., 1978) Clean Water (Clift et al., 1978)

Figure 4.29: The terminal/apparent terminal rise velocity vs. bubble diameter at 3000mm in the
presence of MIBC and NaCl.

73
Figure 4.29 presents apparent terminal rise velocity vs. bubble diameter in the
presence of NaCl and MIBC. The Figure shows the velocities are close and both
reagents (eventually in the case of NaCl) slow down the bubble rise to that
approaching contaminated water. The similarity observed by Quinn et al (2007) is
also found for rise velocity of single bubbles.

Henry et al. (2008) measured the terminal rise velocity of very small single
bubbles (40μm<db<100μm) in the presence of some salts over a similar range of
concentration as here. It was reported that addition of NaCl did not reduce the
rise velocity compared to pure water. But there is a question, whether their data
reflects the terminal velocity as they measured the velocity at a distance of only
ca. 1.5mm above the capillary. According to Figure 4.28 the single bubble does
not attain terminal velocity at such a short distance, indeed the bubble required
3000mm to be even close to the terminal velocity. However, according to Figure
1.2 the addition of any reagent appears does not reduce the bubble rise velocity
for bubbles << 1mm, and therefore a salt effect may not be detectable.

4.6. Comparison of frothers

In this part three industrial frothers were tested: F150, DF250 and MIBC. Figure
4.30 presents the apparent terminal rise velocity vs. bubble diameter in the
presence of these frothers. The velocities are close and comparable to
contaminated water. Figure 4.31 presents the apparent terminal velocity at
3000mm vs. concentration in F150, DF250 and MIBC. It shows that there is a
critical concentration to reach terminal velocity; however their critical
concentrations are very low compared to many of the alcohols. DF250 has the
lowest critical concentration (in ppm).

Sam et al. (1996) measured the terminal rise velocity of two of the current
frothers, DF250 and MIBC. Figure 4.32 presents a comparison between the
results. There is good agreement between the DF250 data with slightly lower
velocities recorded for MIBC in the current work.

74
 40

35

Apparent Terminal Rise Velocity (cm/s) 30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bubble Diameter (mm)
F150 DF250
MIBC Contaminated Water (Clift et al., 1978)
Clean Water (Clift et al., 1978)

Figure 4.30: The terminal/apparent terminal velocity at 3000mm vs. bubble

diameter in the presence of the three commercial frothers.

35

30
Apparent Terminal Velocity (cm/s)

25

20

15

10

F150

5 DF250

MIBC

0
0.001 0.01 0.1 1 10 100
Frother Concentration (ppm)

Figure 4.31: Apparent terminal velocity at 3000mm vs. concentration of single

bubbles in F150, DF250 and MIBC.

75
 25

Terminal Rise Velocity (cm/s) 20

15

10

5 Dowfroth 250 (current work)

Dowfroth 250 (Sam et al.,1996)
MIBC (current work)
MIBC (Sam et al.,1996)
0
0 0.5 1 1.5 2 2.5 3
Bubble Diameter (mm)

Figure 4.32: The comparison of measured terminal rise velocity of MIBC and Dowfroth 250
between the Sam et al. (1996) and the recent work.

4.7. The dependency of terminal velocity on frother properties

Sam et al. (1996) reported that terminal rise velocity is independent of frother
concentration, simply the time taken to reach terminal velocity is increased as
concentration is decreased. In practice however, since time is finite (height of
flotation cell) there are two effective concentration regimes:
i) At lower than critical concentration the frother concentration affects
bubble rise velocity.
ii) At higher than critical concentration the rise velocity is independent of
concentration and is reduced to the contaminated water value.

76
 40

35
Apparent Terminal Velocity (cm/s)
30

25

20

15

350mm
10
1000mm
5 2000mm
3000mm
CC@2000mm CC@1000mm
0
0 50 100 150 200 250 300
1-Pentanol Concentration (ppm)

Figure 4.33: The influence of travel distance of bubble on critical concentration and apparent
terminal velocity in 1-pentanol for ca. 1.45mm single bubbles.

Accordingly, the interpretation of terminal rise velocity first requires determining

the velocity profile.

Regarding the several velocity profiles presented in the current work that
exhibited decreasing trend at the end of profile, it could be concluded that if the
experiment was repeated in a taller column (longer travel distance) the bubble
would reach terminal velocity. The increase in bubble traveling distance gives
enough time to reach sufficient surfactant adsorption to terminal velocity. As a
result in an infinitely tall column the single bubble would reach terminal velocity in
any concentration, in agreement with the conclusion of Sam et al. (1996). The
increase in bubble travel distance shifts the critical concentration to lower
concentrations.

Sam et al. (1996) did note that frother type affected the profile and possibly the
terminal velocity. Figure 4.33 presents the terminal velocity vs. concentration for
the frothers used in this study for ca. 1.45mm bubble size. Figure 4.33 indicates
that above the critical concentration the frother type did not influence terminal
velocity and the terminal velocity approaches that in contaminated water.

77
Figure 4.34 compares the average terminal velocity of the frothers studied at
different bubble size with the clean and contaminated water lines by Clift et al.
(1978). Figure 4.35 indicates that the trend of current work is similar to the trend
of contaminated water line; however, the current work exhibits a consistently
higher terminal velocity.

40

35

30
Terminal Velocity (cm/s)

25

20

15

10

Type
5 Clean Water
Contaminated Water

0
1-Butanol 1-Pentanol 1-Hexanol 2-Hexanol 1-Heptanol 1-Octanol MIBC F150 DF250

Figure 4.34: Comparison of terminal velocity of the used frother with clean and contaminated
water lines by Clift et al. (1978) (ca. 1.5mm).

78
 40

35

Apparent Terminal Rise Velocity (cm/s) 30

25

20

15

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Bubble Diameter (mm)
Big (1.8-1.95mm) Medium (1.4-1.55mm)
Small (0.85-1.0mm) Trend Line of Current Work
Contaminated Water (Clift et al., 1978) Clean Water (Clift et al., 1978)

Figure 4.35: Comparison of the trend line of current work with clean and contaminated water lines
by Clift et al. (1978).

79
CHAPTER FIVE: CONCLUSIONS AND RECOMMENDATIONS
Single bubbles in the size (diameter) range 0.8-2.0 mm were generated under a
low frequency regime (<80 bubbles/min), and the bubble size and rise velocity
over ca. 3500mm were measured using image processing techniques. This
chapter summarizes the conclusions and ends with recommendations for future
work.

5.1. Conclusions

5.1.1. Bubble generation

ƒ The size of bubbles generated at a capillary at low frequency was not
materially influenced by the concentration and type of reagents.

5.1.2. Velocity profile analysis

ƒ The velocity profile was obtained by using a mobile video camera to track
and record individual bubbles.
ƒ The observed velocity profiles showed the typical properties, as first
reported by Sam et al. (1996).
ƒ Determination of true terminal rise velocity requires analysis of the profile
to establish when velocity is constant.
ƒ The “apparent terminal velocity” is introduced that gives the possibility of
comparing with the rise velocity of the bubbles reported in the literature
when distance is known.

5.1.3. Hypothesis based on observation of Azgomi et al. (2007)

ƒ The results of this work confirmed that reagent type can affect the rise
velocity profile of same size bubbles over the concentration range of
interest in flotation, which is in agreement with the previous observations
of Azgomi et al. (2007) and Acuna and Finch (2008).
ƒ The significant difference between rise velocity of F150 and 1-pentanol
shown to be because in the latter bubbles do not reach terminal velocity.
This explains the observation of Azgomi et al. (2007).

80
5.1.4. Aliphatic alcohols
ƒ Over the concentration range used in flotation, 1-butanol and 1-pentanol
approximated the trend of pure water (Clift et al., 1978); i.e., their
presence did not significantly reduce the bubble rise velocity. 1-heptanol
and 1-octanol approached the contaminated water trend.
ƒ On the concentration range of interest in flotation, 1-hexanol proved the
exception: the lowest concentration of hexanol acted like 1-butanol and 1-
pentanol and the higher concentrations exhibited the trend in 1-heptanol
and 1-octanol. Velocity profile analysis showed that the bubble did not
reach terminal rise velocity at the lowest concentration of 1-hexanol.
ƒ Comparison of 1-hexanol, 2-hexanol and MIBC confirmed that not only the
frother concentration could affect the apparent terminal velocity but also
differences in molecular structure. The former impact could be called a
“concentration effect” and the latter “molecular structure effect” that makes
a link between the mechanism of single bubble rise velocity and the
chemistry of surfactant.
ƒ To explore the concentration effect a wider concentration range was
examined and it was observed that there is critical concentration, CC, for
each alcohol to reach terminal velocity by a given distance. Below the CC
surfactant concentration affects the apparent terminal rise velocity, while
over the critical concentration (when the bubble reaches terminal velocity)
the rise velocity is independent of concentration.
ƒ There was agreement with the results of Krzan and Malysa (2002) in the
case of 1-butanol, 1-pentanol and 1-hexanol. However, they considered
the rise velocity at 350mm (35cm) as the terminal velocity where the
results here indicate the bubble does not necessarily reach the terminal
velocity at this distance location.

5.1.5. The comparison of MIBC and NaCl

ƒ Both MIBC and NaCl had similar influence on bubble rise velocity, which
agrees with the gas holdup data reported by Quinn et al. (2007).

81
5.1.6. Commercial frothers
ƒ Three commercial frothers, F150, DF250 and MIBC, were tested and
were found to reach terminal at low critical concentration (<1ppm) and
approximate the contaminated water trend.
ƒ Comparing to results of Sam et al. (1996) the terminal rise velocity in
MIBC and DF250 exhibited good agreement.

5.1.7. Dependency of terminal velocity on frother properties

ƒ The traveling distance of bubble affects the apparent terminal velocity.
The increase in travel distance results in having lower critical
concentration (CC) as more time available for the rising bubble for
reaching terminal velocity. Thus with an infinite travel distance (i.e., very
tall column) the single bubble would reach terminal velocity in any
concentration, which is in agreement with Sam et al. (1996). As the
bubble size increases, the higher critical concentration is required.
ƒ Comparing terminal velocity indicates that the frother type does not affect
terminal rise velocity, practically. As a result when the frother
concentration is sufficient to reach terminal velocity, the terminal velocity
is independent of frother type that is not in agreement with the conclusion
of Sam et al. (1996).
ƒ The influence of reagent on terminal rise velocity is strongly dependent on
bubble size. For bubble size <1mm there was no obvious difference in
rise velocity between any reagents. For the bubble sizes between 1 to
1.5mm the difference increased to a maximum; above 1.5mm the
difference started to decline once more.

5.2. Recommendations for future works

ƒ Most of studies on bubble rise velocity consider physical aspects
(bubble size, method of generation). The results of this work showed
that chemical properties of surfactants of interest in flotation play an
important role, which should be understood.

82
ƒ Study of the influence on bubble rise velocity as a function of structure
of the reagent should be expanded. It seems that the adsorption and
orientation of frother molecules on the bubble surface depends on the
molecular structure, and could influence the number of required
molecules for controlling surface mobility.
ƒ Velocity profile analysis is the only confident method to identify the
true terminal rise velocity. Any future work must include velocity profile
analysis to avoid misinterpretation.
ƒ According to the results of current work it was observed that the
applied concentration equivalency (that was based on equivalent
bubble size production) did not reflect the real impact of frother
concentration on bubble rise velocity. So the suggestions that critical
concentration (CC) concept introduced here can be considered as the
basis for comparing frothers.

83
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98
Appendix
Figure 4.1: Variation of single bubble size vs. bubble frequency
for reagents using 25μm capillary.
Type Frequency (bubbles/min) Bubble Size (mm)
37 0.725
1-Butanol 23 0.774
35 0.713
19.3 0.858
16.7 0.940
1-Pentanol
16.8 0.904
18.1 0.923
18.3 0.843
28.1 0.817
1-Hexanol 22.72 0.785
26.3 0.807
17.65 0.877
28.2 0.785
17.6 0.867
1-Heptanol
19 0.876
17.6 0.888
18.3 0.843
28.1 0.817
1-Hexanol 22.72 0.785
26.3 0.807
17.65 0.877
17.8 0.891
18.5 0.883
1-Octanol
18.18 0.868
18.18 0.877
21.27 0.878
17.6 0.947
MIBC
18 0.877
20 0.926
37 0.700
22 0.827
DF250
28 0.792
35 0.714
34 0.667
14.5 0.976
F150 18 0.991
20.9 0.914
17.6 0.873
18.5 0.927
20.52 0.750
16.5 0.941
NaCl
19.25 0.846
17.03 0.935
19.1 0.861

99
 Figure 4.2: The variation of single bubble size vs. bubble frequency for the three
applied capillaries.

Capillary 25μm Capillary 51μm Capillary 75μm

Frequency Bubble Size Frequency Bubble Size Frequency Bubble Size
(bubbles/min) (mm) (bubbles/min) (mm) (bubbles/min) (mm)
37 0.725 50 1.568 70.58 1.961
23 0.774 50 1.568 75 1.943
35 0.713 51.7 1.563 79.2 1.953
37 0.700 51.8 1.563 79.2 1.975
22 0.827 35.86 1.832 70.58 1.967
28 0.792 51.9 1.571 76.33 1.980
35 0.714 52.88 1.532 80 1.968
34 0.667 55.09 1.527 72.87 1.978
14.5 0.976 53.84 1.524 75.3 1.963
18 0.991 53.78 1.515 77.12 1.943
20.9 0.914 53.88 1.509 70.1 1.919
17.6 0.873 54.07 1.548 75.47 1.959
28.2 0.785 24.23 1.901 73.96 1.978
17.6 0.867 27.9 1.830 84 1.936
19 0.876 51.67 1.562 79.5 1.957
17.6 0.888 52.98 1.493 78.84 1.971
18.3 0.843 56.44 1.571 77.02 1.937
28.1 0.817 53.66 1.519 91 1.914
22.72 0.785 47.39 1.526 65.25 1.969
26.3 0.807 78.5 1.919
17.65 0.877
21.27 0.878
17.6 0.947
18 0.877
20 0.926
18.5 0.927
20.52 0.750
16.5 0.941
16.9 0.956
19.25 0.846
17.03 0.935
19.1 0.861
19.68 0.830
17.8 0.891
18.5 0.883
18.18 0.868
18.18 0.877
19.3 0.858
16.7 0.940
16.8 0.904
18.1 0.923

100
Figure 4.3: Bubble size as a function of equivalent concentration for 25μm capillary.
Equivalent Concentration
Type
1 3 5 6
1-Butanol 0.72 0.71 0.7
1-Heptanol 0.86 0.87 0.89 0.84
MIBC 0.93 0.92 0.92
1-Octanol 0.88 0.86 0.87 0.85
1-Pentanol 0.93 0.91 0.92 0.88

Figure 4.4: An example of velocity profile where bubble reaches terminal velocity
in F150 1ppm for ca. 1.45mm bubble.
Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s)
0 0 718.81 15.76
7.38 22.15 876.71 15.82
24.67 29.72 1035.29 15.90
42.95 25.15 1194.57 15.96
56.76 16.29 1354.95 16.12
68.00 17.43 1597.24 16.17
79.10 15.86 1839.95 16.20
89.86 16.43 2002.76 16.36
105.86 15.79 2166.38 16.36
121.57 15.57 2329.76 16.32
134.57 14.64 2493.67 16.47
152.76 14.50 2658.19 16.44
168.52 14.80 2823.00 16.53
250.86 15.39 2988.48 16.57
405.38 15.52 3093.48 16.61
561.48 15.71

101
 Figure 4.6.a : Velocity profiles in F150 (ca 1.5mm).
1ppm
Distance (mm) Velocity (cm/s) Distance (mm) Velocity (cm/s) Distance (mm) Velocity (cm/s)
0.0 0.0 214.5 19.8 360.6 18.6
1.8 10.8 221.0 19.2 369.5 18.0
8.7 30.6 227.1 18.0 375.1 18.0
19.2 32.4 233.2 19.2 383.6 16.8
30.0 32.4 239.7 19.8 457.0 17.4
40.5 30.6 245.8 18.0 603.3 17.9
51.3 34.2 252.0 19.0 757.5 17.3
62.1 30.6 258.4 18.0 908.6 17.2
72.2 30.0 264.8 19.0 1059.0 17.1
81.8 27.6 274.4 18.6 1212.4 17.9
95.4 27.0 286.6 18.0 1367.3 17.5
111.8 22.2 298.5 17.7 1520.9 17.6
126.5 21.9 310.3 17.7 1674.5 17.5
140.8 21.0 322.6 19.2 1907.4 17.9
155.2 21.0 335.1 18.3
186.9 20.0 347.8 19.8

Figure 4.6.b : Velocity profiles in F150 (ca 1.5mm).

3ppm 5ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 172.7 18.7 0.0 0.0 147.5 17.8
0.2 1.3 175.8 17.6 0.2 0.9 156.7 19.6
4.0 21.3 252.8 17.9 4.1 22.4 162.9 17.4
13.0 32.7 408.2 17.8 12.4 27.5 168.8 18.0
23.6 30.7 564.6 18.6 21.6 27.8 168.8 18.0
33.7 30.0 724.0 18.0 29.8 21.5 246.5 18.4
42.7 24.0 884.1 18.2 35.6 19.0 406.3 18.1
50.3 22.0 1042.2 18.1 40.8 18.0 567.7 18.8
57.0 18.0 1200.9 18.5 46.9 15.0 734.7 19.4
63.3 20.0 1361.0 17.8 53.1 18.6 900.9 18.6
73.1 19.3 1519.9 18.2 62.2 18.0 1064.0 18.6
85.7 18.3 1677.3 18.1 74.2 18.0 1226.1 18.4
98.0 18.7 1915.3 18.1 86.4 18.6 1391.1 19.3
110.6 19.0 104.9 18.4 1558.9 19.0
140.3 17.6 123.3 18.5
166.7 17.3 135.5 18.2

102
 Figure 4.6.c : Velocity profiles in F150 (ca 1.5mm).
10ppm
Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s)
0.0 0.0 138.6 17.0
1.3 8.0 147.2 18.0
5.7 18.0 153.3 18.7
12.1 20.7 162.1 17.0
18.0 14.7 161.9 17.7
23.0 15.3 235.8 18.2
28.3 16.7 395.8 18.3
34.2 18.7 555.8 18.2
40.4 18.7 719.8 19.3
46.6 18.0 882.8 18.0
55.8 18.7 1043.7 18.8
67.7 17.0 1209.3 19.1
79.3 18.0 1377.9 19.4
91.3 18.0 1543.7 18.5
103.3 18.0 1706.1 18.7
115.0 17.0 1867.1 18.1

Figure 4.7.a: Velocity profiles in F150 (ca 1.5mm) over the first 3 seconds.
1ppm 3ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 214.5 19.8 0.0 0.0 172.7 18.7
1.8 10.8 221.0 19.2 0.2 1.3 175.8 17.6
8.7 30.6 227.1 18.0 4.0 21.3 252.8 17.9
19.2 32.4 233.2 19.2 13.0 32.7 408.2 17.8
30.0 32.4 239.7 19.8 23.6 30.7 564.6 18.6
40.5 30.6 245.8 18.0 33.7 30.0
51.3 34.2 252.0 19.0 42.7 24.0
62.1 30.6 258.4 18.0 50.3 22.0
72.2 30.0 264.8 19.0 57.0 18.0
81.8 27.6 274.4 18.6 63.3 20.0
95.4 27.0 286.6 18.0 73.1 19.3
111.8 22.2 298.5 17.7 85.7 18.3
126.5 21.9 310.3 17.7 98.0 18.7
140.8 21.0 322.6 19.2 110.6 19.0
155.2 21.0 335.1 18.3 140.3 17.6
186.9 20.0 347.8 19.8 166.7 17.3

103
 Figure 4.7.b: Velocity profiles in F150 (ca 1.5mm) over the first 3 seconds.
5ppm 10ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 147.5 17.8 0.0 0.0 126.8 18.3
0.2 0.9 156.7 19.6 1.3 8.0 138.6 17.0
4.1 22.4 162.9 17.4 5.7 18.0 147.2 18.0
12.4 27.5 168.8 18.0 12.1 20.7 153.3 18.7
21.6 27.8 168.8 18.0 18.0 14.7 162.1 17.0
29.8 21.5 246.5 18.4 23.0 15.3 161.9 17.7
35.6 19.0 406.3 18.1 28.3 16.7 235.8 18.2
40.8 18.0 567.7 18.8 34.2 18.7 395.8 18.3
46.9 15.0 40.4 18.7 555.8 18.2
53.1 18.6 46.6 18.0
62.2 18.0 55.8 18.7
74.2 18.0 67.7 17.0
86.4 18.6 79.3 18.0
104.9 18.4 91.3 18.0
123.3 18.5 103.3 18.0
135.5 18.2 115.0 17.0

Figure 4.8: The influence of reagent concentration on maximum velocity

in the presence of MIBC, NaCl and F150.
1 3 5 6
MIBC 22 21.82 15.14 11.47
NaCl 20.28 20.16 19.62 17
F150 34.2 32.67 27.79 20.67

104
 Figure 4.9: Velocity profiles in F150, pentanol and tap water (ca 1.5mm).
Tap Water 1-Pen 7ppm-Test 1 1-Pen 7ppm-Test 2 1-Pen 50ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
11.8 17.7 5.1 7.6 2.7 8.0 14.9 35.0
33.8 33.0 26.3 31.8 13.1 31.3 25.9 32.8
56.6 34.3 48.8 33.8 67.8 36.0 37.4 34.6
79.3 34.0 71.7 34.4 79.3 34.7 48.7 33.9
101.8 33.8 94.5 34.2 114.4 36.0 70.9 33.4
124.8 34.6 116.8 33.4 125.8 34.0 82.1 33.5
147.6 34.1 139.7 34.4 146.7 31.3 93.3 33.5
170.4 34.3 162.5 34.2 171.6 37.3 126.9 33.7
191.1 31.0 184.8 33.4 194.2 34.0 171.9 33.7
351.8 34.4 207.3 33.8 217.1 34.3 194.2 33.5
531.1 33.6 229.7 33.6 240.0 34.3 216.5 33.4
665.5 33.6 252.0 33.4 262.7 34.0 238.5 33.0
866.2 33.5 274.3 33.4 285.3 34.0 260.5 33.0
1000.1 33.5 296.5 33.4 296.4 33.3 282.9 33.7
1200.4 33.4 319.3 34.2 307.8 34.0 294.1 33.5
1334.0 33.4 648.3 32.9 319.6 35.3 304.6 31.4
1533.8 33.3 974.0 32.6 330.7 33.3 315.9 33.9
1867.3 33.4 1296.5 32.3 342.4 35.3 580.7 31.2
2000.4 33.3 1957.1 32.0 590.4 33.1 852.6 30.8
2199.8 33.2 2246.8 31.0 878.9 32.7 1120.4 30.3
2332.6 33.2 2551.1 30.4 1160.0 31.8 1394.7 31.1
2532.4 33.3 2845.1 29.4 1445.1 32.3 1654.7 29.4
2665.3 33.2 3080.3 29.4 1715.1 30.6 2168.0 29.1
2865.6 33.4 1445.1 32.3 2430.2 29.7
2998.8 33.3 1715.1 30.6 2679.2 28.2
3109.6 33.2 2925.4 27.9
3168.7 27.5

Figure 4.10: Terminal rise velocity vs. bubble diameter in the presence of F150
and Pentanol compared to swarms results (Acuna and Finch, 2008) and results
for single bubble in clean and contaminated water given by Clift et al. (1978).
Size Velocity
Type
(mm) (cm/s)
0.96 11.27
F150 1.57 16.58
1.98 17.5
0.85 13.17
0.93 14.46
1-Pentanol 1.5 31.2
1.6 29.31
1.94 28.3

105
Figure 4.11: Terminal rise velocity vs. bubble diameter in the presence of low (1)
and high (5) concentrations of pentanol, hexanol and heptanol.
Bubble size (mm) 0.94 1.55 1.93
1-Pentanol- low Apparent terminal Velocity (cm/s) 15.02 29.31 26.95
Standard Deviation (mm) 0.001 0.8 0.08
Bubble size (mm) 0.92 1.53 1.91
1-Pentanol- high Apparent terminal Velocity (cm/s) 14.46 29.2 25.56
Standard Deviation (mm) 0.06 0.5 0.46
Bubble size (mm) 0.81 1.52 1.96
1-Hexanol- low Apparent terminal Velocity (cm/s) 10.75 28.1 25.56
Standard Deviation (mm) 0.96 0.4 0.1
Bubble size (mm) 0.87 1.51 1.94
1-Hexanol-high Apparent terminal Velocity (cm/s) 11.43 17.6 17.32
Standard Deviation (mm) 1.2 0.9 0.4
Bubble size (mm) 0.87 1.53 1.98
1-Heptanol- low Apparent terminal Velocity (cm/s) 13.09 15.99 19.12
Standard Deviation (mm) 0.55 0.1 1.15
Bubble size (mm) 0.89 1.52 1.92
1-Heptanol- high Apparent terminal Velocity (cm/s) 13.4 16.4 16.55
Standard Deviation (mm) 0.04 0.2 0.2

Figure 4.12: The terminal rise velocity vs. bubble diameter in the presence of low
(1) and high (5) concentrations of butanol, hexanol and octanol.
Bubble size (mm) 0.72 1.56 1.96
1-Butanol-
Apparent terminal Velocity (cm/s) 8.41 31 25.62
Equiv. Conc. 1
Standard Deviation (mm) 0.09 0.2 0.08
Bubble size (mm) 0.71 1.56 1.94
1-Butanol-
Apparent terminal Velocity (cm/s) 8.41 30 25.67
Equiv. Conc. 5
Standard Deviation (mm) 0.02 0.2 0.45
Bubble size (mm) 0.81 1.52 1.96
1-Hexanol-
Apparent terminal Velocity (cm/s) 10.75 28.1 25.56
Equiv. conc. 1
Standard Deviation (mm) 0.96 0.4 0.1
Bubble size (mm) 0.87 1.51 1.94
1-Hexanol-
Apparent terminal Velocity (cm/s) 11.43 17.6 17.32
Equiv. conc. 5
Standard Deviation (mm) 1.2 0.9 0.4
Bubble size (mm) 0.88 1.5 1.95
1-Octanol –
Apparent terminal Velocity (cm/s) 14.07 15.32 16.69
Equiv. Conc. 1
Standard Deviation (mm) 0.48 0.08 0.24
Bubble size (mm) 0.89 1.56 1.97
1-Octanol-
Apparent terminal Velocity (cm/s) 15.33 16.69 16.72
Equiv. Conc. 5
Standard Deviation (mm) 0.02 0.44 0.21

106
 Figure 4.13: Velocity profiles in 1-hexanol (ca 1.5mm).
1-Hexanol 5.25ppm 1-Hexanol 37.5ppm
Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 1937.3 18.7
16.9 50.6 6.8 20.5 2115.4 16.9
45.1 34.2 21.4 23.2 2289.8 18.0
68.0 34.3 36.7 22.9 2466.8 17.4
90.9 34.2 52.1 23.2 2644.1 18.0
136.3 34.1 67.2 22.1 2822.1 17.6
181.7 33.7 81.7 21.5 2994.5 16.9
204.2 34.0 95.5 19.6 3103.7 13.3
226.9 33.8 108.5 19.4
249.3 33.4 121.3 19.1
271.9 34.3 134.0 19.1
294.5 33.6 146.9 19.6
316.9 33.4 159.7 18.8
339.1 33.2 172.3 18.8
515.7 33.1 184.6 18.3
845.8 32.9 281.1 18.1
1172.9 32.5 461.5 18.0
1499.8 32.8 648.3 19.4
1817.7 30.7 834.4 17.9
2128.2 31.4 1022.1 19.7
2438.7 30.7 1211.5 18.2
2742.1 29.9 1392.1 17.9
2989.1 27.8 1662.8 18.1

Figure 4.14: The terminal rise velocity vs. bubble diameter in the presence of 1-hexanol and 2-
hexanol.
Bubble size (mm) 0.81 1.52 1.92
1-Hexanol- Equiv.
Apparent terminal Velocity (cm/s) 10.75 28.95 25.56
conc. 1
Standard Deviation (mm) 0.96 0.49 0.1
Bubble size (mm) 0.88 1.52 1.9
1-Hexanol- Equiv.
Apparent terminal Velocity (cm/s) 11.43 17.6 17.32
conc. 5
Standard Deviation (mm) 1.21 0.9 0.4
Bubble size (mm) 0.83 1.52 1.92
2-Hexanol- Equiv.
Apparent terminal Velocity (cm/s) 11 20.8 19.8
conc. 1
Standard Deviation (mm) 0.8 0.24 0.21
Bubble size (mm) 0.85 1.52 1.92
2-Hexanol- Equiv.
Apparent terminal Velocity (cm/s) 11.1 15.87 18.63
conc. 5
Standard Deviation (mm) 0.8 0.19 0.27

107
 Figure 4.15.a: Velocity profiles in butanol (ca 1.45mm).
Tap Water 1-Butanol-11.5ppm 1-Butanol-82ppm 1-Butanol-125ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
5.9 17.7 19.0 38.1 18.0 38.3 6.3 18.8
22.8 33.0 50.0 36.0 48.0 36.0 23.5 33.0
45.2 34.3 74.0 36.0 71.0 33.0 45.7 33.5
67.9 34.0 98.0 36.0 94.0 36.0 68.2 33.8
90.5 33.8 121.0 33.0 118.0 36.0 90.7 33.8
113.3 34.6 144.0 36.0 141.0 33.0 113.3 33.8
136.2 34.1 168.0 36.0 164.0 36.0 135.8 33.8
159.0 34.3 192.0 36.0 187.0 33.0 158.3 33.5
261.1 34.4 215.0 33.0 221.0 34.5 180.7 33.8
441.4 33.6 238.0 36.0 267.0 34.5 203.2 33.5
598.3 33.6 262.0 36.0 301.0 33.0 225.5 33.3
765.8 33.5 286.0 36.0 335.0 34.5 247.7 33.5
933.2 33.5 310.0 36.0 425.0 33.5 270.0 33.3
1100.3 33.4 333.0 33.0 594.0 34.0 292.1 33.0
1267.2 33.4 356.0 36.0 763.0 33.5 314.2 33.3
1433.9 33.3 438.0 35.0 925.0 31.7 488.5 32.6
1700.5 33.4 614.0 35.3 1086.0 33.0 812.2 32.1
1933.8 33.3 791.0 35.5 1252.0 33.3 1131.3 31.7
2100.1 33.2 966.0 34.7 1515.0 32.6 1486.2 31.0
2266.2 33.2 1244.0 34.8 1742.0 32.0 1793.3 30.2
2432.5 33.3 1591.0 34.6 1901.0 31.7 2051.5 29.5
2598.8 33.2 1832.0 34.0 2059.0 31.5 2342.5 28.7
2765.4 33.4 1995.0 31.7 2216.0 31.3 2625.0 27.8
2932.2 33.3 2157.0 33.5 2371.0 30.5 2897.9 26.8
3054.2 33.2 2323.0 33.0 2524.0 30.7
2486.0 32.0 2676.0 30.0
2646 32.00 2825 29.66
2806 32.00 2973 29.50

108
 Figure 4.15.b: Velocity profiles in butanol (ca 1.45mm).
1-Butanol-150ppm 1-Butanol-180ppm 1-Butanol-260ppm
Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0
9.9 29.8 4.4 13.3 13.3 38.2
30.9 33.0 19.5 32.0 37.8 33.0
53.0 33.4 41.0 32.5 59.7 32.8
75.3 33.4 62.9 33.3 81.5 32.8
97.6 33.6 85.0 33.0 103.3 32.5
120.0 33.4 107.0 33.0 125.1 32.8
142.2 33.2 129.0 33.0 146.9 32.8
164.3 33.0 151.0 33.0 168.3 31.4
186.3 33.2 172.9 32.8 189.4 32.1
208.4 33.0 194.8 33.0 210.8 31.8
230.5 33.2 216.6 32.3 232.0 31.8
252.6 33.0 238.3 32.8 253.3 32.1
274.5 32.8 259.8 31.8 274.7 32.1
296.5 33.2 281.1 32.3 296.1 32.3
318.3 32.3 302.7 32.5 317.2 30.9
490.9 32.3 472.8 31.9 482.1 30.9
811.1 31.7 788.1 31.2 783.4 29.4
1126.7 31.4 1311.1 30.6 1081.8 30.3
1588.8 30.5 1768.3 30.1 1375.0 28.3
2040.5 29.3 2006.3 29.5 1654.3 27.5
2330.0 28.6 2297.9 28.8 1924.5 26.5
2611.1 27.7 2582.3 28.1 2181.3 24.8
2884.1 26.9 2859.8 27.4 2425.4 24.0
3071.6 26.4 3049.9 26.6 2660.2 23.0
2886.3 22.2
3040.6 21.6

109
 Figure 4.16.a: Velocity profiles in pentanol (ca 1.45mm).
Tap Water 1-Pentanol-7ppm 1-Pentanol-50ppm 1-Pentanol-110ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
5.9 17.7 2.5 7.6 7.5 35.0 0.9 2.6
22.8 33.0 15.7 31.8 20.4 32.8 10.8 27.2
45.2 34.3 37.5 33.8 31.6 34.6 31.0 27.8
67.9 34.0 60.3 34.4 43.1 33.9 52.2 30.2
90.5 33.8 83.1 34.2 59.8 33.4 67.5 29.9
113.3 34.6 105.7 33.4 76.5 33.5 87.9 30.0
136.2 34.1 128.3 34.4 87.7 33.5 113.2 30.0
159.0 34.3 151.1 34.2 110.1 33.7 133.2 30.2
261.1 34.4 173.7 33.4 149.4 33.7 153.3 30.0
441.4 33.6 196.1 33.8 183.1 33.5 173.2 29.8
598.3 33.6 218.5 33.6 205.4 33.4 193.1 29.8
765.8 33.5 240.9 33.4 227.5 33.0 212.9 29.6
933.2 33.5 263.1 33.4 249.5 33.0 232.8 30.0
1100.3 33.4 285.4 33.4 271.7 33.7 252.6 29.3
1267.2 33.4 307.9 34.2 288.5 33.5 272.2 29.8
1433.9 33.3 483.8 32.9 299.4 31.4 292.2 30.0
1700.5 33.4 811.1 32.6 310.2 33.9 311.9 29.1
1933.8 33.3 1135.3 32.3 448.3 31.2 331.3 29.3
2100.1 33.2 1626.8 32.0 716.6 30.8 350.8 29.3
2266.2 33.2 2101.9 31.0 986.5 30.3 370.3 29.3
2432.5 33.3 2398.9 30.4 1257.5 31.1 522.5 28.5
2598.8 33.2 2698.1 29.4 1524.7 29.4 804.8 28.0
2765.4 33.4 2962.7 29.4 1911.4 29.1 1079.5 27.0
2932.2 33.3 2299.1 29.7 1341.4 25.4
3054.2 33.2 2554.7 28.2 1590.9 24.5
2802.3 27.9 1830.0 23.4
3047.1 27.5 2060.1 22.7
2283.2 22.0
2499.7 21.3
2711.6 21.1
2920.0 20.6

110
Figure 4.16.b: Velocity profiles in pentanol (ca 1.45mm).
1-Pentanol-130ppm 1-Pentanol-250ppm
Distance (mm) Velocity (cm/s) Distance (mm) Velocity (cm/s)
0.0 0.0 0.0 0.0
4.2 12.6 7.2 21.5
15.6 21.4 20.5 18.7
29.6 20.8 32.9 18.5
43.6 21.0 45.3 18.7
57.5 20.8 57.8 18.9
71.3 20.6 70.4 18.7
85.1 20.8 82.9 18.9
98.9 20.6 95.5 18.9
112.5 20.4 108.2 18.9
125.8 19.5 120.8 18.9
138.6 18.9 133.4 18.9
151.0 18.4 146.1 19.2
163.3 18.4 158.8 18.9
175.5 18.2 171.3 18.7
187.7 18.4 183.8 18.9
283.2 17.9 284.6 18.9
457.4 17.0 461.8 16.5
623.9 16.3 623.8 15.9
786.4 16.2 782.5 15.8
947.9 16.1 940.8 15.8
1109.3 16.2 1098.9 15.8
1270.1 16.0 1257.5 15.9
1429.3 15.8 1414.8 15.6
1586.3 15.6 1649.2 15.7
1742.3 15.6 1883.0 15.4
1898.4 15.6 2038.5 15.7
2053.8 15.5 2193.8 15.4
2208.9 15.5 2348.7 15.6
2365.0 15.7 2504.6 15.6
2522.5 15.8 2659.9 15.4
2678.2 15.3 2815.1 15.6
2834.1 15.9 2970.7 15.5
2992.4 15.8 3069.2 15.7
3087.2 15.8

111
 Figure 4.17.a: Velocity profiles in pentanol (ca 1.85mm).
Tap Water 1-Pentanol-7ppm 1-Pentanol-50ppm 1-Pentanol-110ppm
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
11.7 3.9 3.5 10.5 7.8 23.4 5.0 15.0
34.3 19.2 18.2 33.6 27.4 35.4 21.0 33.0
35.7 42.6 41.5 36.3 51.1 35.7 43.2 33.5
36.3 66.6 65.5 35.7 74.8 35.4 65.4 33.3
35.7 90.6 89.6 36.6 98.2 34.8 87.4 32.8
35.0 114.1 113.2 34.2 120.9 33.3 108.9 31.8
35.3 137.6 148.1 35.3 143.2 33.6 129.8 31.0
34.3 160.8 182.9 33.9 165.2 32.4 150.3 30.3
35.0 183.9 205.6 34.2 186.1 30.3 170.3 29.8
34.0 206.9 228.1 33.3 206.8 31.8 190.1 29.8
34.3 229.7 250.8 34.8 227.5 30.3 210.1 30.3
33.7 252.3 272.9 31.5 247.6 30.0 230.3 30.3
33.3 274.7 294.4 33.0 267.4 29.4 250.3 30.0
34.0 297.1 316.4 33.0 287.4 30.6 270.4 30.3
33.0 319.4 484.7 31.5 307.3 29.1 290.5 30.0
32.8 428.8 793.1 30.2 609.2 29.2 448.3 29.6
32.0 591.1 1092.2 29.6 1044.5 28.6 740.1 28.8
31.7 750.1 1386.1 29.2 1327.9 28.1 1020.9 27.4
31.0 999.9 1675.3 28.7 1601.9 26.7 1295.0 27.4
30.4 1215.4 2098.9 28.0 1877.2 28.3 1565.1 26.6
30.3 1367.1 2516.9 27.5 2148.2 25.9 1827.8 26.0
29.8 1607.0 2884.3 26.5 2409.8 26.4 2084.8 25.4
29.4 1814.8 2672.5 26.1 2334.1 24.5
29.2 1961.2 2929.3 25.3 2575.1 23.8
29.0 2106.9 2810.3 23.3
28.9 2338.2 3018.2 22.8
28.7 2452.9
28.4 2623.1
28.1 2735.3
28.0 2903.1
27.8 3014.2
27.6 3106.2

112
 Figure 4.17.b: Velocity profiles in pentanol (ca 1.85mm).
1-Pentanol-130ppm 1-Pentanol-225ppm 1-Pentanol-275ppm
Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0
21.1 31.6 5.2 15.6 7.3 21.9
53.3 33.5 19.5 27.3 22.4 23.4
75.3 32.5 37.0 25.1 36.9 20.1
111.5 28.8 52.7 21.9 49.7 18.3
146.5 29.0 67.5 22.6 62.3 19.6
166.0 29.5 82.4 22.1 75.1 18.8
185.6 29.2 96.9 21.3 87.5 18.3
205.0 29.3 111.0 21.0 99.9 18.9
224.6 29.3 125.1 21.3 112.5 18.9
244.0 29.0 139.4 21.6 125.0 18.5
263.5 29.4 153.6 21.0 137.5 18.9
282.9 28.8 167.4 20.4 150.2 19.3
302.2 29.0 181.4 21.6 162.5 17.7
463.8 30.4 195.5 20.7 174.6 18.6
765.4 29.9 209.1 20.1 187.1 18.8
1047.0 26.4 317.7 20.4 285.5 18.4
1315.3 27.3 517.9 19.7 468.4 18.2
1578.9 25.4 711.3 19.0 647.6 17.7
1833.0 25.4 901.1 18.9 824.1 17.6
2081.4 24.3 1090.9 19.0 998.7 17.3
2320.2 23.5 1280.5 18.9 1172.3 17.4
2552.2 22.9 1526.5 18.2 1346.4 17.4
2782.2 23.1 1709.2 18.7 1561.2 17.4
3010.5 22.6 1831.7 18.3 1735.8 17.5
2013.1 18.0 1867.9 17.1
2284.9 18.2 2039.7 17.3
2557.3 18.1 2212.8 17.3
2736.7 17.8 2385.6 17.2
2915.0 18.1 2558.2 17.3
3053.0 17.8 2730.6 17.2
2903.6 17.4
3049.1 17.5

113
 Figure 4.18.a: Velocity profiles in hexanol (ca 1.45mm).
Tap Water 1-Hexanol-5.25ppm 1-Hexanol-15ppm
Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0
5.9 17.7 16.9 38.2 9.1 27.2
22.8 33.0 45.1 34.2 27.6 28.4
45.2 34.3 68.0 34.3 46.2 27.5
67.9 34.0 90.9 34.2 63.2 27.5
90.5 33.8 136.3 34.1 80.1 27.2
113.3 34.6 181.7 33.7 97.7 25.6
136.2 34.1 204.2 34.0 115.8 28.8
159.0 34.3 226.9 33.8 134.3 26.8
261.1 34.4 249.3 33.4 155.4 26.8
441.4 33.6 271.9 34.3 176.6 27.0
598.3 33.6 294.5 33.6 194.3 25.9
765.8 33.5 316.9 33.4 211.5 25.8
933.2 33.5 339.1 33.2 228.6 25.4
1100.3 33.4 515.7 33.1 245.8 26.3
1267.2 33.4 845.8 32.9 263.2 25.8
1433.9 33.3 1172.9 32.5 280.3 25.7
1700.5 33.4 1499.8 32.8 297.3 25.3
1933.8 33.3 1817.7 30.7 313.9 24.5
2100.1 33.2 2128.2 31.4 330.3 24.6
2266.2 33.2 2438.7 30.7 346.9 24.9
2432.5 33.3 2742.1 29.9 363.3 24.4
2598.8 33.2 2989.1 27.8 379.6 24.5
2765.4 33.4 396.2 25.2
2932.2 33.3 527.5 24.6
3054.2 33.2 773.4 24.6
1012.5 23.2
1242.3 22.8
1515.9 21.8
1732.2 21.1
1892.6 20.8
2098.9 20.4
2301.4 20.0
2500.3 19.7
2794.2 19.5
2987.0 19.3

114
Figure 4.18.b: Velocity profiles in hexanol (ca 1.45mm).
1-Hexanol-25ppm 1-Hexanol-37.5ppm
Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0
8.9 26.6 6.8 20.5
26.5 26.2 21.4 23.2
43.7 25.4 36.7 22.9
60.3 24.3 52.1 23.2
76.5 24.5 67.2 22.1
92.9 24.5 81.7 21.5
109.0 23.7 95.5 19.6
124.9 24.0 108.5 19.4
140.5 23.0 121.3 19.1
155.7 22.6 134.0 19.1
170.7 22.4 146.9 19.6
185.8 22.8 159.7 18.8
201.0 22.7 172.3 18.8
216.2 23.1 184.6 18.3
231.2 21.9 281.1 18.1
344.4 21.2 461.5 18.0
552.0 20.3 648.3 19.4
755.5 20.4 834.4 17.9
957.9 20.1 1022.1 19.7
1158.7 20.1 1211.5 18.2
1351.5 18.5 1392.1 17.9
1563.7 18.0 1662.8 18.1
1742.5 17.7 1937.3 18.7
1890.2 17.7 2115.4 16.9
2057.7 17.6 2289.8 18.0
2229.5 16.8 2466.8 17.4
2400.2 17.3 2644.1 18.0
2573.2 17.3 2822.1 17.6
2745.5 17.2 2994.5 16.9
2916.9 17.1 3103.7 13.3
3053.1 17.0

115
 Figure 4.19.a: Velocity profiles in 1-hexanol (ca 1.85mm).
Tap Water 1-Hexanol-5.25ppm 1-Hexanol-15ppm
Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0
11.7 3.9 6.3 18.9 10.9 32.8
34.3 19.2 24.1 34.6 31.8 29.8
35.7 42.6 47.4 35.2 51.2 28.6
36.3 66.6 70.9 35.2 70.4 28.8
35.7 90.6 93.7 33.3 89.8 29.3
35.0 114.1 115.8 33.0 109.2 28.8
35.3 137.6 137.4 31.8 128.4 28.8
34.3 160.8 158.7 32.0 147.8 29.3
35.0 183.9 179.6 30.8 167.1 28.6
34.0 206.9 200.0 30.4 186.2 28.6
34.3 229.7 220.3 30.8 205.5 29.3
33.7 252.3 240.6 30.0 224.7 28.4
33.3 274.7 260.6 30.0 371.3 27.4
34.0 297.1 280.6 30.0 648.5 28.0
33.0 319.4 300.7 30.3 926.3 27.6
32.8 428.8 456.2 29.1 1197.8 26.7
32.0 591.1 743.6 28.4 1471.7 26.3
31.7 750.1 1025.5 28.0 1732.5 25.8
31.0 999.9 1303.8 27.7 1977.8 25.0
30.4 1215.4 1580.5 27.7 2225.1 24.5
30.3 1367.1 1856.0 27.4 2467.0 23.9
29.8 1607.0 2128.8 27.2 2704.7 23.6
29.4 1814.8 2398.7 26.8 2869.4 23.2
29.2 1961.2 2661.0 25.6
29.0 2106.9 2908.0 24.0
28.9 2338.2
28.7 2452.9
28.4 2623.1
28.1 2735.3
28.0 2903.1
27.8 3014.2
27.6 3106.2

116
 Figure 4.19.b: Velocity profiles in 1-hexanol (ca 1.85mm).
1-Hexanol-25ppm 1-Hexanol-37.5ppm
Distance (mm) Velocity (cm/s) Distance (mm) Velocity (cm/s)
0.0 0.0 0.0 0.0
11.3 33.8 1.3 3.8
33.1 31.7 11.2 26.0
53.6 29.7 27.3 22.3
71.6 24.3 47.3 18.9
87.9 24.8 65.9 18.3
104.4 24.8 75.3 18.0
120.9 24.5 84.8 18.3
137.6 25.7 103.3 18.8
154.1 23.7 121.9 18.3
170.5 25.6 146.3 18.3
187.3 24.7 170.8 18.5
203.6 24.3 266.7 17.9
219.9 24.8 444.7 17.7
236.3 24.5 620.2 17.4
252.7 24.5 794.8 17.5
379.5 23.7 1056.8 17.5
620.2 24.4 1318.9 17.5
862.3 24.0 1581.1 17.5
1101.4 23.8 1843.6 17.6
1335.8 23.1 2018.8 17.5
1571.0 22.5 2193.5 17.5
1795.7 22.5 2368.9 17.6
2010.2 21.9 2544.8 17.6
2228.3 21.7 2721.0 17.6
2444.7 21.6 2897.6 17.7
2658.6 21.2
2869.1 20.9
3022.1 20.8

Figure 4.20: Apparent terminal velocity vs. concentration of single bubbles in 1-butanol.
Current Work- Concentration (ppm) 11 82 125 150 180 260 2500
1.45mm@350mm Velocity (cm/s) 36 34.5 33.4 32.3 32.2 30.9 20
Krzan et al- Concentration (ppm) 148 370 740 2220 2368 7400
1.42mm@350mm Velocity (cm/s) 18 16 16 16 16 16

Figure 4.21: Apparent terminal velocity vs. concentration of single bubbles in 1-pentanol.
Current Work- Concentration (ppm) 7 50 110 130 250
1.45mm@350mm Velocity (cm/s) 33.8 33 29.2 17.6 17.2
Krzan et al- Concentration (ppm) 8.81 44.07 88.15 132.225 264.45 440.75
1.42mm@350mm Velocity (cm/s) 34 31.5 26.5 19 16.5 16.5

117
 Figure 4.22: Apparent terminal velocity vs. concentration of single bubbles in 1-hexanol.
Current Work- Concentration (ppm) 5.25 15 25 37.5
1.45mm@350mm Velocity (cm/s) 33.2 24.5 21.2 18
Krzan et al- Concentration (ppm) 20.43 40.87 71.52 510.9
1.42mm@350mm Velocity (cm/s) 27 19.5 16.5 15.5

Figure 4.23: Apparent terminal velocity (at 3000mm over the capillary) vs. concentration (ppm) of
single bubbles for range of n-alcohols for ca. 1.45mm bubbles.
Concentration (ppm) 11 82 125 150 180 260 2500
1-Butanol
Velocity (cm/s) 32 29.55 26.75 26.4 26.5 21.6 16
Concentration (ppm) 7 50 110 130 250
1-Pentanol
Velocity (cm/s) 29.4 27.6 20.8 15.8 15.6
Concentration (ppm) 5.25 15 25 37.5
1-Hexanol
Velocity (cm/s) 29 19.4 17 16.5
Concentration (ppm) 0.05 1 4.5 33
1-Heptanol
Velocity (cm/s) 31.3 16.5 16.4 15.99
Concentration (ppm) 0.05 0.25 4.5 32
1-Octanol
Velocity (cm/s) 31.3 28.6 16.69 15.32

Figure 4.24: Apparent terminal velocity (at 3000mm over the capillary) vs. concentration (mol/L)
of single bubbles for range of n-alcohols for ca. 1.45mm bubbles.
Concentration (ppm) 0.000149 0.001108 0.001689 0.002027 0.002432 0.003514 0.033784
1-Butanol
Velocity (cm/s) 32 29.55 26.75 26.4 26.5 21.6 16
Concentration (ppm) 7.94E-05 0.000567 0.001248 0.001475 0.002836
1-Pentanol
Velocity (cm/s) 29.4 27.6 20.8 15.8 15.6
Concentration (ppm) 5.14E-05 0.000147 0.000245 0.000367
1-Hexanol
Velocity (cm/s) 29 19.4 17 16.5
Concentration (ppm) 4.3E-07 8.61E-06 3.87E-05 0.000284
1-Heptanol
Velocity (cm/s) 31.3 16.5 16.4 15.99
Concentration (ppm) 3.84E-07 1.92E-06 3.46E-05 0.000246
1-Octanol
Velocity (cm/s) 31.3 28.6 16.69 15.32

Figure 4.25: Apparent terminal velocity (at 3000mm over the capillary) vs. concentration (ppm) for
ca. 1.45 and 1.85mm single bubbles in 1-pentanol and 1-hexanol.
Concentration (ppm) 7 50 110 130 250
1.45mm
Velocity (cm/s) 29.4 27.6 20.8 15.8 15.6
1-Pentanol
Concentration (ppm) 7 50 110 130 225 275
1.85mm
Velocity (cm/s) 26 25.6 23 22.8 17.9 17.5
Concentration (ppm) 5.25 15 25 37.5
1.45mm
Velocity (cm/s) 29 19.4 17 16.5
1-Hexanol
Concentration (ppm) 5.25 15 25 37.5
1.85mm
Velocity (cm/s) 25 23.4 20.85 17.6

118
Figure 4.26: The apparent terminal rise velocity vs. bubble diameter at 3000mm in
the presence of MIBC, 1-hexanol and 2-hexanol.
1-Hexanol- Vel 10.75 28.95 25.56
Equiv. Conc. 1 Size 0.81 1.52 1.92
1-Hexanol- Vel 11.43 17.6 17.32
Equiv. Conc. 5 Size 0.88 1.52 1.9
2-Hexanol- Vel 11 20.8 19.8
Equiv. Conc. 1 Size 0.83 1.52 1.92
2-Hexanol- Vel 11.1 15.87 18.63
Equiv. Conc. 5 Size 0.85 1.52 1.92
MIBC- Vel 10.8 15.46 17
Equiv. Conc. 1 Size 0.91 1.52 1.95
MIBC- Vel 11.08 15.22 16.8
Equiv. Conc. 5 Size 0.91 1.52 1.95

119
 Figure 4.27: Velocity profiles in 2-hexanol (ca 1.5mm).
2-Hexanol-5.25ppm 2-Hexanol-37.5ppm
Distance (mm) Velocity (cm/s) Distance (mm) Velocity (cm/s)
0.0 0.0 0.0 0.0
18.0 27.0 14.0 21.0
36.0 27.0 28.0 21.0
56.0 30.0 44.0 24.0
74.0 27.0 60.0 24.0
92.0 27.0 74.0 21.0
110.0 27.0 88.0 21.0
130.0 28.0 102.0 21.0
148.0 27.0 114.0 21.0
166.0 27.0 128.0 21.0
184.0 27.0 140.0 18.0
202.0 27.0 152.0 18.0
220.0 27.0 166.0 18.0
238.0 27.0 178.0 18.0
256.0 27.0 190.0 18.0
274.0 27.0 372.0 18.2
540.0 26.6 552.0 18.0
798.0 25.8 744.0 19.2
1046.0 24.8 924.0 18.0
1296.0 25.0 1120.0 19.6
1794.0 24.9 1302.0 18.2
2030.0 23.6 1482.0 18.0
2258.0 22.8 1844.0 18.1
2482.0 22.4 2030.0 18.6
2700.0 21.8 2200.0 17.0
2912.0 21.2 2380.0 18.0
3118.0 20.6 2554.0 17.4
2734.0 18.0
2910.0 17.6
3078.0 16.8
3128.0 13.4

Figure 4.28: Apparent terminal velocity vs. concentration of single bubbles in 1-hexanol, 2-
hexanol and MIBC.
Concentration (ppm) 5.25 15 25 37.5
1-Hexanol
Velocity (cm/s) 29 19.4 17 16.5
Concentration (ppm) 5.25 15 25 37.5
2-Hexanol
Velocity (cm/s) 20.8 17.3 16.4 15.87
Concentration (ppm) 0.01 0.05 2.5 20
MIBC
Velocity (cm/s) 31 29.9 15.46 15.22

120
 Figure 4.29: Velocity profiles in MIBC (ca. 1.5mm) and NaCl (ca 1.6mm).
MIBC-Equiv. Conc. 1 MIBC-Equiv. Conc. 5 NaCl-Equiv. Conc. 5 NaCl-Equiv. Conc. 1
Distance Velocity Distance Velocity Distance Velocity Distance Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
8.9 13.3 7.1 10.6 8.2 12.4 8.2 12.4
29.4 30.9 24.5 26.2 30.9 34.1 30.9 34.1
52.0 33.9 41.3 25.1 54.5 35.3 54.5 35.3
73.7 32.6 57.8 24.8 76.9 33.7 76.9 33.7
94.9 31.7 73.5 23.5 97.5 30.9 97.5 30.9
116.3 32.1 88.9 23.2 118.2 31.1 118.2 31.1
156.6 30.2 104.0 22.6 138.2 30.0 138.2 30.0
176.6 30.0 118.7 22.1 156.7 27.7 156.7 27.7
195.4 28.3 132.4 20.5 176.9 30.4 176.9 30.4
213.1 26.6 144.5 18.3 196.0 28.6 196.0 28.6
230.6 26.1 157.1 18.8 214.7 28.1 214.7 28.1
260.6 22.5 168.7 17.5 234.0 28.9 234.0 28.9
274.6 21.0 180.0 16.9 253.5 29.3 253.5 29.3
621.4 17.3 191.6 17.5 271.3 26.6 271.3 26.6
778.6 15.7 203.1 17.2 290.2 28.4 290.2 28.4
933.1 15.5 363.3 16.0 546.2 25.6 546.2 25.6
1086.0 15.3 518.4 15.5 764.0 21.8 764.0 21.8
1238.6 15.3 670.5 15.2 968.5 20.4 968.5 20.4
1390.9 15.2 822.7 15.2 1165.5 19.7 1165.5 19.7
1995.1 15.1 972.7 15.0 1357.5 19.2 1357.5 19.2
2146.3 15.1 1121.6 14.9 1896.5 18.0 1896.5 18.0
2298.3 15.2 1269.1 14.7 2067.2 17.1 2067.2 17.1
2451.1 15.3 1418.4 14.9 2402.0 16.7 2402.0 16.7
2598.3 14.7 1714.2 14.8 2571.6 17.0 2571.6 17.0
2750.0 15.2 1865.8 15.2 2747.5 17.6 2747.5 17.6
2902.3 15.2 2017.5 15.2 2919.8 17.2 2919.8 17.2
3056.3 15.4 2169.8 15.2 3091.2 17.1 3091.2 17.1
2320.9 15.1
2471.5 15.1
2622.7 15.1
2776.0 15.3
2928.9 15.3
3081.6 15.3

121
 Figure 4.30: The apparent terminal rise velocity vs. bubble diameter at 3000mm in the presence
of MIBC and NaCl.
MIBC NaCl
Size Velocity Size Velocity
(mm) (cm/s) (mm) (cm/s)
0.91 11.25 0.91 10.8
1.52 15.46 1.6 17.05
1.95 16.8 1.99 17.5

Figure 4.31: The apparent terminal rise velocity vs. bubble diameter at 3000mm in
the presence of the three commercial frothers.
MIBC F150 DF250
Size Velocity Size Velocity Size Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.91 11.25 0.96 11.27 0.69 8.67
1.52 15.46 1.57 16.58 0.81 9.5
1.95 16.8 1.98 17.5 1.56 16.45
1.96 18.2

Figure 4.32: Apparent terminal velocity vs. concentration of single bubbles in F150, DF250 and
MIBC.
Concentration (ppm) 0.01 0.05 2.5 20
MIBC
Velocity (cm/s) 31 29.9 15.46 15.22
Concentration (ppm) 0.003 0.015 0.06 1 10
F150
Velocity (cm/s) 30.45 21.5 16.6 16.55 16.5
Concentration (ppm) 0.0232 0.06 0.9 3 25
DF250
Velocity (cm/s) 16.7 16.5 16.5 16.5 16.4

Figure 4.33: The comparison of measured terminal rise velocity of MIBC and Dowfroth 250
between the Sam et al. (1996) results and the recent work.
MIBC Dowfroth 250 Dowfroth 250 MIBC
(Sam et al.,1996) (Sam et al.,1996) (current work) (current work)
Size Velocity Size Velocity Size Velocity Size Velocity
(mm) (cm/s) (mm) (cm/s) (mm) (cm/s) (mm) (cm/s)
0.96 12.07 0.96 11.61 0.69 8.67 0.91 11.25
1.4 16.6 1.4 15.87 0.81 9.5 1.52 15.46
2.2 19.8 2.2 18 1.56 16.45 1.95 16.8
2.7 21.8 2.7 21 1.96 18.2

Figure 4.34: The influence of travel distance of bubble on critical concentration and rise velocity in
1-pentanol for ca. 1.45mm single bubbles.
Concentration (ppm) 0 7 50 110 130 250
350mm
Velocity (cm/s) 34 33.8 33 29.2 17.6 17.2
Concentration (ppm) 0 7 50 110 130 250
1000mm
Velocity (cm/s) 34 32.3 30.3 26.96 16.17 15.8
Concentration (ppm) 0 7 50 110 130 250
2000mm
Velocity (cm/s) 34 31.04 29.1 22.65 15.5 15.6
Concentration (ppm) 0 7 50 110 130 250
3000mm
Velocity (cm/s) 34 29.4 27.6 20.8 15.3 15.5

122
Figure 4.35: Comparison of terminal velocity of the used frother with clean and
contaminated water lines by Clift et al. (1978) (ca. 1.5mm).
Terminal Velocity
Type
(cm/s)
Clean Water 34.5
Butanol 16
Pentanol 15.6
1-Hexanol 16.5
2-Hexanol 15.87
Heptanol 15.99
Octanol 15.32
MIBC 15.22
F150 16.5
DF250 16.4
Contaminated Water 18.5

Figure 4.36: Comparison of the trend line of current work with clean and
contaminated water lines by Clift et al. (1978).
Big Medium Small
Size
(1.8-1.95mm) (1.4-1.55mm) (0.85-1.0mm)
18.2 16 8.4
17.5 16.45 8.67
16.55 16.2 11.27
17.32 16.5 11.3
Data
16.8 15.87 11.25
17.5 15.46 10.8
16.72 16.5 13.17
17.5 16.5 14.25
Average 17.26 16.19 11.14
Standard
0.54 0.38 1.98
Deviation

123