Chapter 2

Degradation of Reactive Red 120 dye using

hydrodynamic cavitation and photographic

analysis of cavitational behavior inside a

cavitating device
Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

2.1 Introduction

Waste water from the textile industry containing dyes causes serious
environmental problem due to their intense color and potential toxicity. About 10-
20% of the total dyestuff used in the dyeing process is released into the environment
(Akpan and Hameed, 2009; Cho and Zoh, 2007). The waste water containing colored
solution is the source of aesthetic pollution, eutrophication, and perturbations in
aquatic life essentially due to their organic nature. Among all types of dyes used in the
textile and paper industry around 50-70% dyes are of Azo class (Cho and Zoh, 2007;
Song et al., 2009; Kusic et al., 2006). Colored waste streams from azo dye production
processes and industries involved in their utilization pose a major threat to the
surrounding ecosystems due to the documented health hazards caused by toxicity and
a potentially carcinogenic nature of such organic pollutants (Nilsson et al., 1993).
Therefore, the necessity of effective dye wastewater treatment prior to discharge into
the effluent is undoubtedly important. One of the major difficulties in treating this
type of colored wastewater is the ineffectiveness of biological processes, which are
mostly economically suitable processes in comparison with other treatment options
(Costa et al., 2004). Azo dyes are known to be largely non-biodegradable in aerobic
conditions and can be reduced to more hazardous intermediates in anaerobic
conditions (Baughman and Weber, 1994). Other common commercial processes, such
as coagulation/flocculation and adsorption, do not involve chemical transformations,
and therefore generally transfer waste components from one phase to another, thus
causing secondary loading of environment (Papic et al., 2000; Forgacs et al., 2004;
Herrera et al., 2001).

Therefore, it is necessary to find an effective treatment technology that leads

to complete destruction of the dye molecules, in terms of limited water recourses
management and the need for nature preservation. An attractive, sludge free
alternative for the treatment of wide range of organic pollutants present in wastewater,
including synthetic dyes, are so called Advanced Oxidation Processes (AOPs).
Hydroxyl radicals (OH•), highly reactive species generated in sufficient quantities by
AOPs, have the ability to oxidize the majority of the organics present in the

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

wastewater effluents. Common AOPs involve Fenton and Fenton like processes,
cavitation (acoustic and hydrodynamic cavitation), ozonation, electrochemical
oxidation, photolysis with H 2 O 2 and O 3 , TiO 2 photocatalysis, radiolysis, and various
combinations of these methods (Papic et al., 2009; Wang et al., 2008; Peternel et al.,
2007; Wu and Chang, 2006; Kusic et al., 2006; Konstantinou and Albanis, 2004; Hua
and Hoffmann, 1997; Sivakumar and Pandit, 2002). Though, highly successful on
laboratory scale, these AOPs find less application on industrial scale due to their high
cost of fabrication and maintenance and also due to their design constraints on larger
scale.

Cavitation is one such recent technique which has been found to be

substantially beneficial in wastewater treatment (Adewuyi, 2001). Cavitation is able
to induce and enhance various chemical and physical effects. Application of
cavitation includes, for example, the acceleration of chemical reactions (Javed et al.,
1995; Lieken Jie and Lam, 1995), the cleaning of surfaces (Gallego-Juarez et al.,
2010), the formation of emulsions (Abismail et al., 1999), and the production of
amorphous nanoparticles (Gedanken, 2004). In the field of wastewater treatment, the
positive effects of cavitation have been investigated (Gogate, 2008).

There are four general methods for generating cavitation which differ in their
manner of energy input (acoustic, hydrodynamic, particle induced and optical)
(Lauterborn, 1997). The most widely used form is the generation with ultrasound
(acoustic cavitation). Ultrasonic waves were generated by using different transducers
(piezoelectric/ magneto-strictive). The formation and the continuous growth of
cavitation nuclei take place, due to change in expansion and compression (rectified
diffusion) (Crum, 1984). When the bubbles reach a critical size, they finally collapse.
Though sonochemical reactors have been reported to be highly successful on
laboratory scale operation, these still have been not able to find application on an
industrial scale mostly due to comparatively higher costs of treatment and problems
associated with efficient operation at levels of power dissipation required for
treatment (Mason, 2000). On one hand, it is difficult to scale up an ultrasonic device
due to variation in the acoustic field and the difficulty to calculate it (Gogate and

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

Pandit, 2004c). On the other hand, there exist various opinions about the energy
efficiencies of acoustic cavitation. In last decade a new way of generating cavities
namely, hydrodynamic cavitation and its application in the field of wastewater
treatment have been explored by many researchers. There are not many studies on the
applications of hydrodynamic cavitation to disintegrate water pollutants (Wang et al.,
2009; Bracutigam et al., 2009; Sivakumar and Pandit, 2002; Chakinala et al., 2008).
But this technique has several advantages, which makes it a useful technique for the
industrial wastewater treatment application. Hydrodynamic cavitation has potential of
application on larger scale due to its capability in generating hydroxyl radicals at
ambient condition, easy to scaleup and less material cost makes it more economical.

In hydrodynamic cavitation, cavities are formed by passing the liquid through

the constriction/geometry provided in line such as venturi, orifice plate etc. When the
pressure at the throat or vena-contracta of the constriction falls below the vapor
pressure of the liquid, the liquid flashes, generating number of cavities that
subsequently collapse when the pressure recovers downstream of the mechanical
constriction. The effects of cavity collapse are in terms of creation of hot spots,
releasing highly reactive free radicals, surface cleaning and/or erosion, and
enhancement in local transport (heat, mass and momentum) rates. The collapse of
bubbles, generates localized ‘‘hot spots’’ with transient temperature of the order of
10,000 K, and pressures of about 1000 atm (Didenko et al., 1999). Under such
extreme conditions water molecules are dissociated into OH• and H• radicals. These
OH• radicals then diffuse into the bulk liquid medium where they react with organic
pollutants and oxidize/mineralize them. The two main mechanisms for the
degradation of pollutants using hydrodynamic cavitation are the thermal
decomposition/pyrolysis of the volatile pollutant molecules entrapped inside the
cavity during the collapse of the cavity and secondly, the reaction of OH• radicals
with the pollutant occurring at the cavity-water interface. In the case of non volatile
pollutant the main mechanism for the degradation of pollutants will be the attack of
hydroxyl radicals on the pollutant molecules at the cavity-water interface and in the
bulk fluid medium. The mechanical effects are also significant. In some cases the
intensity of shockwaves generated by the collapsing cavity can break molecular

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

bonds, especially the complex large molecular weight compounds. The broken down
intermediates are more amenable to OH• attack as well as biological oxidation, which
can further enhance the rate of oxidation/mineralization of the pollutants.

In the present work the degradation of Reactive Red 120 dye (RR120) has
been carried out using self-designed hydrodynamic cavitation set-up. The RR120 is of
azo class and most of the synthetic dyestuffs found in this class are recalcitrant to the
biodegradation. Shaul et al. (1991) studied biodegradation of 18 azo dyes and found
that 11 dyes are practically unchanged through the activated sludge system, 4 were
adsorbed by the activated sludge and only 3 were biodegraded, resulting in the release
of these substances into water bodies. A significant remainder of about 40-70% of
COD and color in textile finishing industry effluents after conventional biological
treatment requires an advanced treatment for improving the quality (Arslan et al.,
1999; Zhang et al., 2004). The retention of COD even after the conventional
biological process is due to the complex nature of most of the dyes and due to the
formation of more stable intermediates during the biological treatment and thus
requires advanced treatment processes than can completely oxidize such pollutants.

The aim of this study was to understand the hydrodynamic characteristics of

the cavitating device and the dynamic behavior of cavities (cavity formation, cavity
growth and cavity collapse) inside a hydrodynamically cavitating device (circular
venture) in view of analyzing the optimum operating parameters for getting maximum
degradation of RR120. The effect of operating parameters (inlet pressure and
cavitation number), solution pH and addition of H 2 O 2 on the degradation rate has
been studied. In this study, two important operating parameters (inlet pressure and
cavitation number) for a cavitational device have been optimized in order to get
maximum cavitational effects. The photographic study was carried out to observe the
cavity behavior inside the cavitating device (venturi), which offers a plausible
explanation to the observation of the optimum operating conditions.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

2.2 Material and methods

2.2.1 Materials

Reactive Red 120 dye (molecular weight: 1470 g/mol; molecular formula:
C 44 H 24 Cl 2 N 14 Na 6 O 20 S 6 ) was a gift sample from ATUL limited India, and hydrogen
peroxide was purchased from S.D. fine chemicals (India). The chemical structure of
Reactive Red 120 dye is shown in Figure 2.1. The experiments were carried out
within the temperature range of 30 to 35˚C. All the solutions were prepared with tap
water as a dissolution medium. The concentration of dye was kept constant in all the
cases at 34μM (50 ppm). The concentration range of H 2 O 2 was kept in the range of 0
to 3400 μM and added externally.

N
NaO 3S
N SO 3Na

SO3 Na OH

NaO 3S NaO3 S
NH
H
N HN N N
OH N N
N N N
N N Cl
H
Cl
SO3 Na
Reactive Red 120

Figure 2.1: Molecular structure of Reactive Red 120

2.2.2 Hydrodynamic cavitation reactor

The experimental setup is shown in Figure 2.2. The setup includes a holding
tank of 15 liter volume, a positive displacement pump of power rating 1.1 kW, control
valves (V1, V2, and V3), and flanges to accommodate the cavitating device in the
main line and a bypass line to control the flow through the main line. The suction side
of the pump is connected to the bottom of the tank and discharge from the pump

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

branches into two lines; the main line and a bypass line. The main line consists of a
flange which houses the cavitating device which can be either orifice or a venturi. The
main line flow rate was adjusted by changing the number of piston strokes per unit
time of the pump, which affects the total flow generated. Additionally, a valve is also
provided in the bypass line to control the liquid flow through the main line. Both the
mainline and bypass line terminate well inside the tank below the liquid level to avoid
any induction of air into the liquid due to the falling liquid jet. Figure 2.3 shows one
of the cavitating device (venturi) used in this work. Two different types of materials
were used in the fabrication of venturi. A transparent venturi made-up from acrylic
was used for the photographic study and a metal venturi made-up from brass was used
for the rest of the experiments.

Main
line
Cooling Bypass P2
water out line
Venturi

P1
Cooling Tank
V2 V3
water in

V1
Pump

P1, P2 - Pressure gauges

V1,V2,V3 - Control valves

Figure 2.2: Schematic representation of hydrodynamic cavitation reactor set-up

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

2mm
22.61° 6.4°
17mm

10mm 18mm 67mm 10mm

Figure 2.3: Schematic of cavitating device (circular venturi)

2.2.3 Experimental and Analytical Methods

Hydrodynamic cavitation based degradation of RR120 was carried out at

different conditions using fixed solution volume of 6 liter and for a constant
circulation time of 3h. The typical concentration of the dye in the real industrial
wastewater is found to be in the range of 10-150 ppm (Papic et al., 2009) and hence
an initial concentration of RR120 was kept constant in all the cases at 34 μM (50ppm)
to establish the kinetic and for optimization of different operating parameters. The
temperature of the solution during experiments was kept constant in all the cases at
about 35°C and was maintained by circulating cooling water through the jacket
provided to the holding tank. The photographs were taken using digital camera
(Canon EOS 1000D model). The shutter speed was kept 1/2600 sec as it was found to
be adequate to capture the fast moving cavity and also gave adequate illumination.
The absorbance of RR120 was monitored using UV-Spectrophotometer (Shimadzu-
1800) and then the concentration of dye was calculated by analyzing the absorbance
of dye solution at the wavelength of 513 nm. All the experiments were repeated at
least two times and the reported values are average of the different experimental runs.
The experimental errors were within ± 5% of the reported value of the extent of
degradation or reaction rate constant and error bars are shown in the figures. The
complete mineralization was analyzed by measuring the Total Organic Carbon (TOC)
content of dye solution using TOC Analyzer with 8 port auto sampler (OCT-L;
Shimadzu Corporation, Japan). Separate calibration charts were prepared for
determination of Total Carbon (TC) and Inorganic Carbon(IC), so that TOC could be

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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analyzed as TOC=TC-IC. TOC values reported represent the average of at least two
measurements per sample and third measurement has been carried out by the TOC
analyzer if coefficient of variation in earlier two samples is greater than 2 %. The
standard deviation of 0.2 was kept constant for all the cases during measurement of
TOC.

2.3 Results and discussion

2.3.1 Hydraulic characteristics

The hydraulic characteristics of the cavitating device (venturi) has been

studied by measuring the main line flow rate and by using a dimensionless parameter
called as Cavitation number (C V ). The inlet pressure to the venturi as well as flow
through the main line was adjusted by changing the number of piston strokes per unit
time. The Cavitation number is a dimensionless number used to characterize the
condition of cavitation in hydraulic devices (Moholkar and Pandit, 1997; Gogate and
Pandit, 2000; Shah et al., 1999). The cavitation number is defined as

 
p −p 
CV =  2 v 
 ρv 2
1 
 
 2 
o

Where, p 2 is the fully recovered downstream pressure, p v is the vapor pressure of the
liquid, v o is the velocity at the throat of the cavitating constriction which can be
calculated by knowing the main line flow rate and diameter of the venturi or orifice.
Under ideal condition cavities are generated at a condition C v ≤1 but in many cases
cavities are known to get generated at a value of C v greater than one due to the
presence of some dissolved gases and suspended particles which provide additional
nuclei for the cavities to form (Shah et al., 1999). The cavitation number at which first
cavity appears is called cavity inception number (C vi ). Figure 2.4 shows the effect of
the pump discharge pressure (venturi inlet pressure) on the main line flow rate and
cavitation number. The sample calculation for the estimation of cavitation number is
shown in appendix 2A for the inlet pressure of 5 bar.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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600 3

500 2.5

Cavitation Number (Cv)

Flow Rate (lit/hr)

400 2

300 Flow Rate

1.5
Cavitation Number
200 Cvi = 0.45 1

100 0.5

0 0
0 1 2 3 4 5 6 7 8 9 10 11
Inlet Pressure(bar)

Figure 2.4: Effect of inlet pressure on the main line flow rate and Cavitation
Number (C V )

The liquid flow rate through the main line increases with an increase in the
pump discharge pressure. It was found that cavitation number decreases with an
increase in inlet pressure to the venturi. An increase in the discharge pressure
increases the flow through the main line, the velocity at the throat of the venturi also
increases, which subsequently reduces the cavitation number as per the definition of
C v . The first clear cavity formation i.e., cavity inception number was found to be 0.45
(inlet pressure, 1 bar). The number of cavities generated increases with a decrease in
cavitation number i.e. with an increase in the liquid velocity. Yan and Thorpe (1990)
reported the cavitation number for the inception of cavity for different orifice sizes.
They observed that for a given size orifice, the cavitation inception number remains
constant within an experimental error for a specified liquid. The cavitation inception
number does not change with the liquid velocity and is a constant for a given orifice
size and is found to be increasing with an increasing size and dimension of the orifice.
Moholkar and Pandit (1997) have discussed this observation in terms of increased
turbulent fluctuating velocity magnitude and its variation with the orifice dimensions.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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2.3.2 Photographic analysis of cavitating device

To study the cavitational behavior inside a cavitating device (venturi)

photographs were taken at different venturi inlet pressures (Figure 2.5(a-f)). The inlet
pressure to the venturi was gradually increased from the lowest possible inlet pressure
until some very small bubbles (cavities) could be seen intermittently. These bubbles
seemed to form at the throat of venturi and were seen at the edge (perimeter) of the
venturi and just downstream of the throat of venturi. This condition was defined as
cavitation inception, i.e. the first cavitation bubble formation (Figure 2.5a, C v = 0.45).
It was observed that with an increase in the venturi inlet pressure (reduction in C v ) the
number density of cavities increases. As the venturi inlet pressure increases cavitation
number decreases and with the decrease in cavitation number more number of cavities
are formed (Figure 2.5(a-c)). Initially at lower pressure the number density of cavities
are low and these cavities behave as individual cavities and they collapse as soon as
they come out on the downstream of the throat of the venturi. No cavity cloud was
observed up to 5 bar venturi inlet pressure (C v =0.15) as till this value of the inlet
pressure the volume fraction occupied by the cavity is quite low and each cavity tends
to behave individually. At the operating condition of inlet pressure of higher than 5
bar, number density of cavities becomes so high that entire downstream area is filled
with cavities and these cavities then start coalescing with each other and form a cavity
cloud (Figure 2.5(d-f)). The first clear cavity cloud was observed at 6 bar pressure
(C v =0.13) and with further increase in inlet pressure almost entire downstream area is
filled with cavity cloud. The condition of cavity cloud formation is called Choked
Cavitation (Sawant et al., 2008). Once choking occurs, a thick vaporous cavity cloud
is detected throughout the downstream of the venturi and length of the cavitation
cloud zone extends further downstream from the throat of the venturi with further
increase in pressure. The occurrence of cavity cloud depends on the several
geometrical and operating parameters as well as on physico-chemical properties of the
liquid such as size and shape of the cavitating device, operating pressure and
cavitation number, density and vapor pressure of the liquid, etc.. Yan and Thorpe
(1990) have shown both experimental and theoretical aspects of this flow regime
transitions caused by cavitation when water is passing through an orifice. They have

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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shown that how the transition occurs from single-phase to two-phase bubbly flow
(cavitation inception) and then from two-phase bubbly flow (cavitation inception) to
two-phase annular jet (central liquid core covered by annular vapor cloud) flow
(choked cavitation). They have calculated the cavitation inception number
experimentally and have shown that the cavitation number at inception is independent
of the liquid velocity but strongly dependent on the size and shape of the geometry.
Hence cavitation inception number does not change with the liquid velocity and is a
constant for a given orifice plate. They have also explained that the minimum pressure
at which cavitation inception occurs was found to be well above the vapor pressure
and the formation of the small bubbles (cavities) at cavitation inception number is due
to desorption of gas upon pressure reduction. Yan and Thorpe (1990) have also
developed a correlation for the cavitation number at which choked cavitation occurs
and found good agreement between experimental and theoretical value. The cavitation
number at the choked cavitation is a function of the ratio of orifice diameter to the
pipe diameter only. They have measured the pressure at the vena contracta and found
out that choked cavitation occurs when the minimum pressure (pressure at the throat
or vena contracta) approaches the vapor pressure and vaporization of the liquid
becomes dominant at choked cavitation.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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(a) P = 1 bar, Cv = 0.45, vo = 20.78m/sec (b) P = 3 bar, Cv = 0.21, vo = 30.06 m/sec

Cavity cloud

(c) P = 5 bar, Cv = 0.15, vo = 36.2 m/sec (d) P = 6 bar, Cv = 0.13, vo = 39.35 m/sec

Cavity cloud Cavity cloud

(e) P = 8 bar, Cv = 0.1, vo = 43.33 m/sec (f) P = 10 bar, Cv = 0.09, vo = 46.42 m/sec

Figure 2.5: Photographs showing the development of cavities downstream of the

cavitating device (circular venturi)

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

2.3.3 Dye Degradation kinetics

In the case of hydrodynamic cavitation, the degradation of dye is due to the

oxidation of dye molecules by OH• radical attack and/or by the thermal decomposition
of dye molecules entrapped inside the collapsing cavity. As mentioned earlier, in the
case of non volatile compound the main mechanism for the destruction of pollutant is
the attack of OH• radicals on the pollutant molecules and most investigators (Lin et
al., 1996; Gül and Özcan-Yıldırım, 2009; Wu, 2008; Adewuyi, 2001) have observed
that it follows the first order kinetics.

To correlate the observed data, pseudo first order kinetics was assumed and
rate constants for the decolorisation as well as for the mineralization process were
calculated using the following equation.

C 
ln O  = k × t
 C 

Where, C is the concentration of dye in mol/lit, k is the rate constant (min-1) and t is
the time in minutes.

Figure 2.6 shows the plot of ln(C O /C) v/s time (t). The plot of ln(C O /C) v/s
time (t) is a straight line passing through the origin, which confirms that the
degradation of RR 120 using hydrodynamic cavitation is showing a first order
reaction kinetics .

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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0.06

0.05

0.04
ln(CO/C)

0.03

0.02

0.01

0.00
0 20 40 60 80 100 120 140
Time(min)

Figure 2.6: First order degradation of RR120 (Conditions: volume of solution: 6

lit, inlet pressure: 3 bar, initial concentration: 34 μM, pH of solution: 7.3).

2.3.4 Effect of inlet pressure

The venturi inlet pressure affects the cavitational condition inside the
cavitating device. The number of cavities being generated and the cavitational
intensity (collapse pressure magnitude) depends very much on the inlet pressure. To
study the effect of the venturi inlet pressure on the degradation of RR120,
experiments were carried out at different inlet pressure ranging from 3 to 10 bar. The
initial concentration of dye and pH was adjusted at 34 μM and 7.3 respectively.
Figure 2.7 shows the effect of inlet pressure on the degradation rate of RR120.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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18
16
Rate Constant x 10^4 (1/min)

14
12
10

8
6
4
2
0
0 1 2 3 4 5 6 7 8 9 10 11

Inlet Pressure(bar)

Figure 2.7: Effect of inlet pressure on degradation rate of RR120 (Conditions:

volume of solution: 6 lit, initial concentration: 34 μM , pH of solution: 7.3)

It was observed that the degradation rate increases with an increase in the inlet
pressure reaching a maximum (5bar) and then drops. The local energy dissipation rate
and the intensity of turbulence increases with an increase in the inlet pressure, thereby
increasing the collapse intensity. The increase in cavitational intensity results into
increased degradation rate of dye. The reduction in degradation rate beyond 5 bar inlet
pressure can be attributed to the condition of choked cavitation as discussed earlier.
As the pressure increases, more number of cavities are formed resulting into the
formation of vapor cloud, thereby decreasing the collapse pressure or intensity of the
cavitational collapse event and hence the extent of the degradation of the dye. The
photographic study of venturi also depicts a similar trend that at an operating
condition of pressure higher than 5 bar, choked cavitation occurs (see Figure 2.5(a-f))
which is also in accordance with the optimum (highest degradation kinetic rate
constant) found by experimental analysis. Under choked cavitation condition, the
vaporous cavities are formed and they do not collapse and carried away with flowing
liquid and then condenses in the water, thus dissipating energy in the liquid, only in

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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the form of increased liquid temperature. Thus, the number of collapsing cavities
decreases with the formation of vaporous cavities (choked cavitation) and hence the
number of hydroxyl radical formed due to dissociation of water molecule under
extreme cavitating conditions (high temperature and pressure) created by the
collapsing cavities are also decreased, which causes a decrease in degradation rate due
to lesser number of hydroxyl radicals available. Sawant et al. (2008) have studied the
effect of hydrodynamic cavitation on killing of zooplankton. They have observed that
at choked cavitation number condition, very large numbers of cavities are generated.
Such a large number of cavities tend to damp the energy released by the neighboring
cavity collapse. Thus, the net energy available for cell disruption decreases and the
zooplankton killing rate reduces. Hence cavitation device should always be operated
at a cavitation number higher than choked cavitation number as it generates maximum
cavitational intensity and cavities collapse individually, giving the most effective
energy utilization.

Senthilkumar and Pandit (1999) have also shown that with an increase in the
venturi inlet pressure the pressure drop across the venturi also increases, resulting in
an increase in the cluster collapse pressure. They have also found that the cluster
collapse pressure or the cavitational intensity increase with an increase in the inlet
pressure reaching to the maximum and then decreases for the reason specified above.
The observation reported in Figure 2.7 is consistent with the above discussion and
earlier similar observations.

2.3.5 Effect of cavitation number (C v )

Figure 2.8 shows the effect of Cavitation number on degradation of RR120. It

was observed that the rate of degradation increases with a reduction in Cavitation
number, reaches a maximum and then drops. The maximum degradation rate was
achieved at a Cavitation number of 0.15 (achieved at an operating pressure of 5 bar).
As the cavitation number decreases, more number of cavities are generated (Vichare
et al., 2000). The increase in the number of cavitational collapse pressure pulses and
OH• radicals thus generated also increase, resulting into an increased degradation rate.
The degradation rate decreases with further decrease in cavitation number (at a

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
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cavitation number C V < 0.15). This may be because of reduced cavitational intensity
due to excess numbers of cavities inside the venturi at very low cavitation number.
Once the cavitation device is completely filled with a lot of cavities (choked
cavitation) these cavities start coalescing to form a larger cavitational bubble (cavity
cloud). These larger bubbles escape the liquid without collapsing or result into an
incomplete collapse, thus reducing the cavitational yield (reduced degradation rate
after C V < 0.15) in terms of the reduced generation of OH• radicals. Where, the
cavitational yield can be defined as number of molecules degraded per unit energy
dissipated.

18

16
5 bar
Rate Constant x 10^4 (1/min)

14
6 bar
12

10
10 bar
8 4 bar
7 bar
6 3 bar
4

0
0 0.05 0.1 0.15 0.2 0.25
Cavitation Number (Cv)

Figure 2.8: Effect of cavitation number on degradation rate of RR120

(Conditions: volume of solution: 6 lit, initial concentration: 34 μM , pH of
solution: 7.3)

SenthilKumar et al. (2000) have carried out decomposition of aqueous KI

solution using hydrodynamic cavitation. They have shown that iodine liberation
increases with a decrease in cavitation number, reaches to the maximum and then
drops. The optimum cavitation number found in their work was in the range of 0.15 to

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0.25 for all the orifice plates studied in their work, which is similar to the optimum
found in our work using venturi.

2.3.6 Effect of solution pH

The effect of medium pH was investigated by carrying out experiments at

different pH in the range of 2-11. All the experiments were carried out at 5 bar venturi
inlet pressure and 34 μM initial dye concentration. Figure 2.9 shows the effect of pH
on the degradation rate of RR120.

90
Rate Constant x 10^4 (1/min)

80
70
60
50
40
30
20
10
0
2 3 4 5.4 7.3 9
pH of Solution

Figure 2.9: Effect of solution pH on degradation rate of RR120 (Conditions:

volume of solution: 6 lit, initial concentration: 34 μM , inlet pressure: 5bar)

The results indicate that the rate of degradation increases with a decrease in
solution pH i.e. acidic medium is more favorable for the degradation of dye. Much
lower degradation rate was observed at pH 10.0. About 60 % decolorisation and 28 %
reduction in TOC was obtained in 3 h at pH 2.0 using HC operating at 5 bar pressure.
The enhancement in the degradation rate at lower pH can be attributed to the fact that
dye molecule is present in the molecular state at lower pH. In its molecular state, dye
molecule becomes more hydrophobic, and hence can easily locate or prefer to be at

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

the gas–water interface of the collapsing cavities. At the interface of cavities, the dye
molecule is then subjected to the direct attack of OH• radicals, resulting into increased
degradation rate. Whereas in the basic medium (pH >7.0) the dye molecules get
ionized and become hydrophilic in nature, thereby remain in the bulk liquid. Due to
the recombination of OH• radicals, only a small fraction of the generated OH• radicals
diffuse into the bulk resulting into lower concentration of OH• radicals being used and
made available for the oxidation of the dye as only about 10% of the OH• radicals
generated in the cavity can diffuse into the bulk solution (Goel et al., 2004). This
causes a reduction in the rate of degradation. Ince and Guyer (2004) have studied this
effect and hence the subsequent impacts of pH and molecular structure on ultrasonic
degradation of azo dyes. They have explained that the acceleration in decolorisation
of dye by acidification is due to neutralization of the dyes upon protonation of
negatively charged SO 3 - sites, and the hydrophobic enrichment of the molecules to
enhance their reactivity under ultrasonic cavitation. While percentage reduction in
decolorisation under alkaline conditions is a consequence of ionization of the dyes by
hydrogen loss from protonated sites and naphthol–OH, resulting in enhanced
hydrophilic character to the dye, which does not accumulate at the cavity-water
interface and hence is not affected significantly by the cavitational event.

Another reason for getting maximum degradation rate under acidic conditions is
possibly due to the slower recombination of generated OH• radicals into the less
reactive H 2 O 2 and also lower pH resist the scavenging of generated OH• radicals by
other ionic species present into the solution such as HCO 3 - and CO 3 2- (Alaton et al.,
2002, Hua and Hoffmann, 1997).

2.3.7 Effect of H 2 O 2

In the case of hydrodynamic cavitation based degradation of dye, the

controlling mechanism is the free radical attack. The use of H 2 O 2 should enhance the
degradation rate due to the generation of additional free radicals. Figure 2.10 shows
the effect of the addition of H 2 O 2 on the degradation rate of RR120. Different molar
ratios of dye to H 2 O 2 concentration were selected ranging from 2.5 times to 100
times. All the experiments were carried out at 5 bar venturi inlet pressure and 34 μM

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

initial dye concentration and at pH 2 for a fixed time (180 min) of operation. It was
observed that the degradation rate of dye increases with an increase in the
concentration of H 2 O 2 . Almost 100 % decolorisation and 60 % reduction in TOC was
obtained at 2040 μM concentration of added H 2 O 2 (ratio of 1:60) as compared to only
60 % reduction in color and 28% reduction in TOC in case of no H 2 O 2 (HC only).
There was no further enhancement in the rate of degradation of dye after 2040 μM
concentration of added H 2 O 2 and also no improvement in percentage reduction of
TOC was observed after 2040 μM concentration of H 2 O 2 . Thus, the optimum
concentration of hydrogen peroxide can be considered as 2040μM, which gives a
molar ratio of 60:1 (H 2 O 2 : dye concentration). The addition of H 2 O 2 provides the
additional OH• radicals for the oxidation of dye molecules, which causes increase in
degradation rate. The scavenging of the OH• radicals is continuously taking place
during the treatment time by H 2 O 2 itself and due to the presence of other scavenging
species such as oxygen, SO 4 2- ions and due to recombination of OH• radicals.
Therefore, the combined effect of HC and H 2 O 2 will be very much dependent on the
utilization of the generated free radicals by the dye molecules. It was also observed
that only 13.15 % decolorisation takes place in 3 h with normal stirring (no HC) and
with the addition of 2040 μM H 2 O 2 . A more quantitative way of evaluating any
synergistic effect, when multiple processes are used, is by reference to a synergy
coefficient, namely,

 k ( HC + H 2O2 ) 
Synergy coefficient =  
 k HC + k H 0 
 2 2 
Synergy coefficient values >1 indicate the combined process exceeds the sum of the
separate processes. The synergy coefficient was found to be 11 for this case
indicating, the combination of HC and H 2 O 2 gives better result (synergistic effect) as
compared to individual operation of these advanced oxidation process, because
hydrodynamic cavitation enhances the micro mixing and thereby increases the
effective utilization of OH• radicals generated through H 2 O 2 by pollutant molecule
and also capable in generating OH• radicals.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

Rate Constant x 10^3 (1/min) 120

100

80

60

40

20

0
0 85 170 340 680 1020 1360 1700 2040 3400
(only
HC)
[H2O2], mM

Figure 2.10: Effect of H 2 O 2 addition on degradation rate of RR120 (Conditions:

volume of solution: 6 lit, initial concentration: 34 μM, pH of solution: 2.0, inlet
pressure: 5 bar)

Teo et al. (2001) have also reported a similar conclusion about the effect of
H 2 O 2 on the degradation of p-chlorophenol using ultrasound. They have reported that
the degradation rate increases with an increase in the hydrogen peroxide concentration
reaching to the maximum at 20 mM concentration of H 2 O 2 for an initial concentration
of 0.4 mM (giving an optimum molar ratio of 50:1) which is very similar to the
optimum found in this work.

2.3.8 Mineralization study

The final products from the oxidation of dye are some intermediates, CO 2 and
H 2 O. These intermediates are expected to be aromatic compounds which also
accounts for the TOC of the solution. Zhang et al. (2007) have carried out study on
the decomposition pathway and reaction intermediate formation of the Reactive Red
120 dye during ozonation. they have found that various aromatic compounds are
formed such as Phenol, 1,2-dihydroxysulfobezene, 1-hydroxysulfonbezene, 4,6-
diamino-1,3,5-triazine-2-ol, 2,4-diamino-6-chloride-1,3,5-triazine and 2,4-hydroxy-6-

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

chloride-1,3,5-triazine. Therefore the measurement of dye concentration

spectrophotometrically does not guarantee the complete mineralization of dye as it
only gives the reduction in color. Mineralization is the complete oxidation of dye
molecule into CO 2 and H 2 O. So, in order to observe the complete mineralization of
dye, TOC was measured at different optimized parameters. Figure 2.11 shows the
percentage reduction in TOC with respect to time for the dye solution treated by HC
alone and by HC + H 2 O 2 .

It was found that TOC reduced by 28 % of the original while 60 %

decolorisation was observed when the degradation was carried out with hydrodynamic
cavitation alone. The addition of H 2 O 2 enhances the TOC removal, around 60% TOC
(100% decolorisation) is reduced by the addition of 2040 μM of H 2 O 2 in combination
of HC at pH 2.0. It was also observed that the decolorisation of dye is a relatively
faster process as compared to the mineralization process. The rate constant for the
declorisation and mineralization (i.e. TOC reduction) processes was found to be
7.54×10-3 min-1 and 2.5×10-3 min-1 respectively when the degradation was carried out
in hydrodynamic cavitation alone and it increases to 95.5×10-3 min-1 and 14.3×10-3
min-1 with the addition of 2040 μM of H 2 O 2 . Almost 100 % decolorisation is
achieved within 15 minutes, whereas 60 % reduction in TOC was observed after 90
min with the addition of 2040 μM of H 2 O 2 in the case of HC. Madhavan et al. (2010)
have also observed that TOC removal rate was much less than that of the
decolorisation process under the same experimental conditions due to the formation of
more stable intermediates in the process of decolorisation.

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

70

60
% Reduction in TOC

50

40

30

20

10

0
0 50 100 150 200
Time (min)

only HC HC + 2040μM H2O2

Figure 2.11: % Reduction in TOC as a function of time at different optimized

conditions (conditions: volume of solution: 6 lit, initial concentration: 34 μM, pH
of solution: 2.0, inlet pressure: 5 bar)

2.4 Conclusions

In this work the degradation of Reactive Red 120 dye was carried out using
hydrodynamic cavitation. Effects of different process variables such as inlet pressure,
Cavitation number, solution pH and addition of H 2 O 2 on the degradation kinetics
were studied. The following important conclusions can be drawn from the present
work.

The rate of degradation was found to be dependent on the venturi inlet

pressure and cavitation number. Inlet pressure and the cavitation number are the two
important operating parameters in the case of hydrodynamic cavitation which affects
the cavitational condition inside the venturi, hence the degradation rate of the dye.
The photographic study shows that at an operating venturi inlet pressure higher than 5
bar, choked cavitation occurs which results into reduced cavitational yield and hence

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

cavitation device should be operated at a cavitation number higher than choked

cavitation to get the maximum effect.

The degradation of RR120 was found to be pH dependent and acidic medium

was found to be favorable for the higher degradation. It was found that operating pH,
state of molecule (whether molecular or ionic) and nature (hydrophobic and
hydrophilic) are the important parameters which ultimately decide the efficient
degradation of pollutants. It has been found that almost 28%
degradation/mineralization of RR120 can be achieved using HC with 60 %
decolorisation taking place in 3 hr and mineralization was further increased to 60%
(100% decolorisation) with the addition of 2040 μM of H 2 O 2 in combination with
HC.

The addition of H 2 O 2 enhances the degradation rate due to additional

hydroxyl radicals available for the oxidation of dye and shows a synergy. However,
this has also an optimum concentration of H 2 O 2 beyond which, no further
enhancement was observed.

Appendix 2A: Sample calculation for the estimation of cavitation number

Inlet fluid pressure = 601325 Pa

Downstream pressure (p 2 ) = 101325 Pa

Vapor pressure of water at 30°C (p v ) = 4242.14 Pa

Volumetric flow rate (V) = 410 LPH

= 1.14 × 10-4 m3/s

Diameter of the throat of the venturi (d o ) = 2 mm

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Chapter 2: Degradation of Reactive Red 120 dye using hydrodynamic cavitation and
photographic analysis of cavitational behavior inside a cavitating device

π
Flow area (a o ) = d o2
4

π
= × (2 × 10 −3 ) 2 = 3.14 × 10-6 m2
4

V 
Velocity at the throat of the venturi (v o ) =  
 ao 

 1.14 ×10 −4 
=  −6
 = 36.30 m/s
 3.14 ×10 

( p 2 − pv )
Cavitation number (C v ) =
1 2
 ρvo 
2 

=
(101325 − 4242.14) = 0.15
1 2
 ×1000 × 36.30 
2 

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