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Journal of Food Engineering 66 (2005) 171–176

www.elsevier.com/locate/jfoodeng

Effects of flow rate, temperature and salt concentration on


chemical and physical properties of electrolyzed oxidizing water
Shun-Yao Hsu
Graduate Institute of Food Science and Technology, National Taiwan University, P.O. Box 23-14, Taipei 106, Taiwan, ROC
Received 15 August 2003; accepted 1 March 2004

Abstract
This study adopted a three-factor-three-level factorial design to study the effects of water flow rate, salt concentration and water
temperature on pH, oxidation–reduction potential (ORP), total residual chlorine, dissolved oxygen, electrical conductivity and
salinity of electrolyzed oxidizing water (EOW). Results indicated that pH and dissolved oxygen concentration were not affected by
these processing factors. Increasing water flow rate decreased total chlorine concentration and ORP of the EOW. Increasing salt
concentration increased total chlorine concentration and electrical conductivity of the EOW. Water temperature had minor effect on
total chlorine concentration. The variations can be well described by linear or quadratic polynomial models.
 2004 Elsevier Ltd. All rights reserved.

Keywords: Electrolyzed oxidizing water; Flow rate; Salt concentration; Temperature; Total residual chlorine concentration

1. Introduction Generation of EOW, in general, involves reactions in


a cell containing inert positively charged (anode) and
Electrolyzed oxidizing water (EOW) has been re- negatively charged (cathode) electrodes, respectively,
ported to have strong bactericidal effects on many separated by a membrane, and through which a dilute
pathogenic bacteria (Buck, van Iersel, Oetting, & Hung, salt solution passes. By subjecting the electrodes to di-
2002; Hayashibara, Kadowaki, & Yuda, 1994; Iwasawa, rect current voltage, negatively charged ions such as
Nakamura, & Mizuno, 1993; Iwasawa, Nakamura, hydroxide and chloride in the salt solution move to the
Nakamura, & Murai, 1993; Kim, Hung, & Brackett, anode to give up electrons and become oxygen gas,
2000, 2001; Shimizu & Hurusawa, 1992; Venkitana- chlorine gas, hypochlorite ion, hypochlorous acid and
rayanan, Ezeike, Hung, & Doyle, 1999b). Major hydrochloric acid, while positively charged ions such as
advantages of using EOW for inactivation of bacteria hydrogen and sodium move to the cathode to take up
are less adverse impact on the environment and no need electrons and become hydrogen gas and sodium
to transport and store potentially hazardous chemicals hydroxide. As a result, two types of water possessing
(Nakagawara et al., 1998). EOW has been widely used in different characteristics are generated. An electrolyzed
medical applications such as prevention of infection of basic solution (pH > 11 and oxidation–reduction po-
methicillin resistant Staphylococcus aureus (MRSA), for tential ðORPÞ < 800 mV) is produced from the cath-
various agricultural purposes such as sterilization of ode side, which has strong reducing potential and may
vegetables, and in food processing industry or house- be used as a cleaning solution. An electrolyzed acid
hold kitchens for disinfection of food materials and food solution (pH < 2:7 and ORP > 1100 mV and presence
processing utensils (Al-Haq, Seo, Oshita, & Kawagoe, of hypochlorous acid) is produced from the anode side,
2001, 2002; Fabrizio, Sharma, Demirci, & Cutter, 2002; which has strong oxidation potential and bactericidal
Izumi, 1999; Kim, Hung, Brackett, & Lin, 2003; Park, effect and can be used as a disinfectant.
Hung, Doyle, Ezeike, & Kim, 2001; Venkitanarayanan, Although many studies showed good bactericidal ef-
Ezeike, Hung, & Doyle, 1999a). fects of EOW, there were few reports on the effects of
processing factors on chemical and physical properties
of EOW generator. Therefore, we investigated the effect
of processing factors on efficiency of EOW generation
E-mail address: gifsthsu@ntu.edu.tw (S.-Y. Hsu). (Hsu, 2003) and the effects of storage conditions on
0260-8774/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2004.03.003
172 S.-Y. Hsu / Journal of Food Engineering 66 (2005) 171–176

chemical and physical properties of EOW (Hsu & Kao, electric currents under these conditions were in the
in press) in previous studies. The purpose of this study ranges of 7.9–15.7 V and 7.40 to 7.69 A, respectively
was to investigate the effects of water flow rate, salt (Hsu, 2003).
concentration and water temperature on pH, oxidation– There were two priority modes (acid–water mode and
reduction potential (ORP), total residual chlorine, dis- alkaline–water mode) in the ARV EOW Generator.
solved oxygen, conductivity and salinity of EOW. Acid–water priority mode was chosen for this study.
According to the ARV EOW Generator, input water
flow was evenly divided into cathode and anode sides of
2. Materials and methods the electrolysis cell while salt solution was totally di-
rected into the anode side during the acid–water mode
2.1. Preparation of electrolyzed oxidizing waters of operation. Therefore, salt concentration in the anode-
side solution could be calculated accordingly (Table 1).
Electrolyzed oxidizing waters (EOW) were prepared The machine was operated at each designated conditions
by electrolysis of double-distilled water (DDW) com- (Table 1) for at least 5 min to reach a steady state before
bining with an adjunct salt solution in an ARV EOW 1 l of EOW sample was collected in a 1-l brown glass
Generator (Aqua-Refine 0.6 L Super, ARV Company bottle covered with a polyvinyl chloride screw cap and a
Ltd., Shinshiro-shi, Aichi-ken, Japan) at designated Teflon pad. The samples were left in room temperature
operation conditions (Table 1). Salt solution (283.6 g (25–30 C) overnight for stabilization purpose prior to
salt in 1 l brine solution) was used as an electrolysis be used for further analytical measurements.
adjunct, which was prepared by dissolving 313.5 g of
edible salts (>99.5% NaCl without any additive, Taiwan 2.2. Analytical measurements of EOW
Salt Industrial Co., Tainan, Taiwan) in 1 l of DDW.
Conductivity of the salt solution was 250 mS/cm. DDW Conductivity and salinity of the EOW were measured
was generated using a DDW Generator (Lotun-A4S, using a Conductivity Meter (Cond 315i, Wissenschaftlich-
Chao-Chung Scientific Co. Ltd., Taipei City, Taiwan, Technische Werkst€atten GmbH & Co., Germany). Oxi-
ROC). The water was stored in 30-l polyethylene storage dation–reduction potential (ORP) and pH of the EOW
tanks before used in one week. Ice cubes made from were measured using a pH/mV/ISE Meter (model SP-
DDW and boiling DDW (at around 95 C) were used to 2200, Suntex Instruments Co., Ltd., Taipei Hsien, Tai-
adjust DDW temperature to designated levels (Table 1) wan, ROC) equipped with a Redox Electrode (Inlab
prior to electrolysis. Flow rates of DDW and saturated 501, Mettler-Toledo International Inc., Greifensee,
salt solution (Table 1) were independently adjusted Zurich, Switzerland) and a pH Electrode (Inlab HA405-
using control valves on the EOW generator. The fluc- DPA, Mettler-Toledo International Inc., Greifensee,
tuation of water temperatures under these conditions Zurich, Switzerland). Dissolved oxygen concentration
were within ±2 C. The operating electric potentials and of the EOW was measured using an Oxygen Meter

Table 1
Operation conditions for manufacturing electrolyzed oxidizing waters
Run number Water flow rate (ml/min) Water temperature (C) Saturated NaCl solution NaCl concentration (g/l)a
flow rate (ml/min)
1 600 25 7.5 6.87
2 600 25 2.7 2.50
3 800 34 4.6 3.21
4 400 34 4.6 6.35
5 280 25 7.5 14.33
6 600 10 7.5 6.87
7 600 40 7.5 6.87
8 400 16 4.6 6.35
9 600 25 7.5 6.87
10 600 25 12.2 11.11
11 400 16 10.3 13.91
12 800 34 10.3 7.13
13 400 34 10.3 13.91
14 936 25 7.5 4.44
15 800 16 4.6 3.21
16 800 16 10.3 7.13
17 600 25 7.5 6.87
a
NaCl concentration of the anode-side solution ¼ saturated NaCl solution flow rate · 0.2836/(saturated NaCl solution flow rate + water flow
rate/2).
S.-Y. Hsu / Journal of Food Engineering 66 (2005) 171–176 173

(Oxi 330i, Wissenschaftlich-Technische Werkst€atten 18


y = 1.0616x + 1.4035
GmbH & Co., Germany). Total residual chlorine (free 16
R2 = 0.9891

Conductivity (mS/cm)
and combined chlorine) was measured according to the 14
12
iodometric method (American Public Health Associa-
10
tion, 1975).
8
6
2.3. Statistical designs and analyses 4
2
This study adopted a three-factor central composite 0
0 2 4 6 8 10 12 14 16
design (Joglekar & May, 1987; Myers, 1971, Chap. 7) to Salt concentration (g/liter)
investigate the effects of water flow rate, water temper-
ature and salt concentration on physical and chemical Fig. 1. Changes of EO water conductivity with respect to salt con-
centration of input solution.
properties of EOW. In practice, the EO water generator
appeared to be unstable at one of the star point in the
central composite design (Run number 5 in Table 1). 12
Therefore, that sample was considered to be an outlier y = 0.6539x + 0.387
10
and the data were eliminated from the data set for fur- R 2 = 0.9907

Salinity (g/kg)
ther statistical analyses. The experiment was indepen- 8
dently conducted twice. Data from the independent 6
replicate trials were pooled and analyzed by analysis of
variance tests and regression analyses (SAS, 1995). 4

0
3. Results and discussion 0 2 4 6 8 10 12 14 16
Salt concentration (g/liter)
Electrical conductivity and salinity of the electrolyzed Fig. 2. Changes of EO water salinity with respect to salt concentration
oxidizing water (EOW) increased linearly with increases of input solution.
in salt concentration of the input (anode-side) solution
(Table 2; Figs. 1 and 2, respectively). Conductivity and
salinity were good indicators of NaCl concentration of 12
the EOW. It was shown in a previous study (Hsu, 2003) y = 0.6154x - 0.4724
10
that about 46% of chloride ions remained in the EOW R 2 = 0.9997
Salinity (g/kg)

after electrolysis. High salt concentration of input 8


solution resulted in high salt concentration and high 6
conductivity of EOW. Salinity was linearly correlated to
4
conductivity (Fig. 3).
Dissolved oxygen (DO) concentration of the EOW 2

varied in the range of 11.6–21.3 ppm, and was not af- 0


0 2 4 6 8 10 12 14 16 18
fected by flow rate, salt concentration and temperature
Conductivity (mS/cm)
(Table 2). Two hundred milliliters each of salt solutions
similar to the anode-side solutions (Tables 1 and 3) were Fig. 3. Relationship between conductivity and salinity of EOW.

Table 2
Effects of water flow rate, salt concentration and water temperature on conductivity, salinity and dissolved oxygen concentration (DO) of EO water
Source Conductivity (mS/cm) Salinity (g/kg) DO (mg/l-O2 )
Linear ** ** –
Quadratic * * –
Cross-product – – –
Total regressed ** ** –
Lack of fit – – –
Total effect of
Water flow rate – – –
Salt concentration ** ** –
Temperature – – –
Ranges 3.96–16.5 2.0–9.7 11.6–21.3
(–) Not significant at a ¼ 0:05 level; (*) significant at a ¼ 0:05 level and (**) significant at a ¼ 0:01 level, n ¼ 2.
174 S.-Y. Hsu / Journal of Food Engineering 66 (2005) 171–176

Table 3
Comparisons on dissolved oxygen (DO) concentration and pH of input salt solutiona and EOW
Run number NaCl (g/l) Temperature (C) DO (mg/l-O2 ) pH
Salt solution EOW Salt solution EOW
1 6.87 25 4.8 13.8 5.79 2.51
2 2.50 25 5.2 14.1 5.90 2.56
3 3.21 34 5.6 13.6 5.92 2.52
4 6.35 34 6.1 13.6 6.12 2.35
6 6.87 10 4.2 15.7 5.52 2.46
7 6.87 40 6.1 15.5 6.07 2.45
8 6.35 16 5.1 18.4 5.54 2.33
9 6.87 25 5.7 16.3 5.93 2.43
10 11.11 25 5.7 15.7 5.93 2.47
11 13.91 16 5.2 18.3 5.91 2.30
12 7.13 34 6.3 14.5 6.06 2.47
13 13.91 34 6.2 16.5 6.19 2.31
14 4.44 25 4.7 16.3 5.72 2.62
15 3.21 16 5.1 16.5 6.20 2.54
16 7.13 16 5.1 17.1 5.72 2.54
17 6.87 25 5.7 15.9 5.93 2.51
a
Using equivalent concentration of salt solution prepared separately.

prepared separately and their pH and ORP were mea- control pH and/or ORP of their output EOW. This was
sured for comparison purpose. As shown in Table 3, usually done by direct control of the electric current
electrolysis significantly increased DO concentration of and/or electric voltage of the electrolysis process or by
the EOW probably due to generation of oxygen gas at indirect control of flow rate of the adjunct salt solution
the anode side. Since part of the oxygen gas had been (Hsu, 2003).
vaporized, the amount remained in EOW might not ORP of the EOW varied in the range of 1140–1160
reflect the amount generated. mV (Table 4). ORP decreased with increases in water
Electrolysis also decreased pH value of EOW (Table flow rate (Fig. 4). However, significant lack-of-fit of the
3) probably due to generations of chlorine gas, hypo- quadratic model (Table 4) indicated that other factor,
chlorous acid and hydrochloric acid. As shown in Table such as machine control action of the EOW machine,
4, flow rate, salt concentration and temperature did not could have affected ORP levels of the EOW.
affect pH probably due to control action of the EOW Total residual chlorine as determined by the iodo-
generator. metric method was significantly affected by water flow
ORP, pH and free chlorine concentration are rate, salt concentration and water temperature (Table 4
important quality indices of EOW. Some reference cri- and Figs. 5–7). Total residual chlorine increased with
teria of pH < 2:7, ORP > 1100 mV and free chlorine increases of salt concentration and decreases of water
concentration of 10–80 ppm had been referred for EOW flow rate. Increasing salt concentration increased chlo-
(Anonymous, 1997; Shimizu & Hurusawa, 1992; Ven- ride concentration of input water while decreasing flow
kitanarayanan et al., 1999a). In order to meet the cri- rate increased residence time of the electrolyte in the
teria, many of the EOW generators had been designed to electrolysis cells. Both increased degrees of electrolysis

Table 4
Effects of water flow rate, salt concentration and water temperature on pH, oxidation–reduction potential (ORP) and total residual chlorine con-
centration of EO water
Source pH ORP (mV) Chlorine (mg/l-Cl2 )
Linear – ** **
Quadratic – – *
Cross-product – – –
Total regressed – ** **
Lack of fit – ** –
Total effect of
Water flow rate – ** **
Salt concentration – – **
Temperature – – **
Ranges 2.14–2.77 1140–1160 8.6–79.1
(*) Significant at a ¼ 0:05 level and (**) significant at a ¼ 0:01 level, n ¼ 2.
S.-Y. Hsu / Journal of Food Engineering 66 (2005) 171–176 175

1170
1160
1150
ORP (mV)

1140
1130
y = -0.0206x + 1161.5
1120 R 2 = 0.627
1110
1100
300 400 500 600 700 800 900 1000
Water Flow rate (ml/min)

Fig. 4. Changes of EO water oxidation–reduction potential (ORP) with


respect to salt concentration of input solution.

Fig. 7. Response surface plots of total residual chlorine concentration


of EO water with respect to salt concentration and temperature of
input solution.

In summary, water flow rate affected total residual


chlorine concentration and ORP of the EOW. Salt
concentration affected total chlorine concentration and
electrical conductivity of the EOW. Water temperature
affected total chlorine concentration. These variations
can be described by linear or quadratic polynomial
models.

Fig. 5. Response surface plots of total residual chlorine concentration Acknowledgement


of EO water with respect to water flow rate and salt concentration of
input solution.
The National Science Council of the ROC (Taiwan)
Government had funded this study (project no. NSC-90-
2214-E-002-036).

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