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Water Air Soil Pollut (2016) 227: 10

DOI 10.1007/s11270-015-2685-y

Removal of Chlorine and Chlorinated Organic Compounds


from Aqueous Media Using Substrate-Anchored Zero-Valent
Bimetals
Kiriro G. Nduta & Isaac W. Mwangi &
Ruth W. Wanjau & J. C. Ngila

Received: 9 April 2015 / Accepted: 11 November 2015 / Published online: 4 December 2015
# Springer International Publishing Switzerland 2015

Abstract Chlorine added to drinking water as a disin- concentration, effect of time and bimetal dosage varia-
fectant is a concern of this generation. This is because tion were established using synthetic water samples. It
chlorine reacts with dissolved organic compounds to was found that the substrate-anchored ZVB material had
form polychlorinated complexes that are carcinogenic. a degradation capacity of 4.532, 5.362 and
Available methods for the removal of chlorine and chlo- 4.513 mol l1 for 1,2-dichloroethane, 2-chloro-2-
rinated compounds include adsorption, precipitation, methylpropane and 1-chlorobutane, respectively. The
electrolysis and ozonation, but some result in the gener- material was then applied on real samples sourced from
ation of more toxic compounds. This study explored the Nairobi. Quantification of chlorine was done using po-
use of zero-valent bimetals Fe/Zn for the degradation of tentiometric methods and the results confirmed that the
chlorinated compounds in water which did not generate degradation was first order. The degradation capacities
toxic by-products. The zero-valent bimetallic material were found to be 2.370.01, 3.550.01 and 3.720.01
was anchored on a polystyrene waste material as a green in that order.
method of cleaning the environment. It was prepared
through nitration, amination, complexation and reduc- Keywords Polystyrene . Chlorination . Zero-valent
tion. The resulting solid material was characterised bimetals . Degradation . Reduction
using Fourier transform infrared (FTIR). The material
was also characterised using XPS which confirmed the
presence of metals anchored on the material through
1 Introduction
complexation. The metals were also found to be present
upon reduction to zero valence and even after the deg-
Water for drinking purposes is normally sourced from
radation process of the chlorinated organic compounds.
rivers, dams and groundwater in its raw form and may
It was then applied for the removal process.
contain substantial amounts of impurities. Such water is
Optimization parameters such initial halide
treated so as to remove the associated contaminants to
ascertain its quality and that it is fit for consumption.
K. G. Nduta : I. W. Mwangi (*) : R. W. Wanjau
Among the treatment processes of water is the use of
Chemistry Department, Kenyatta University, P.O. Box 43844, flocculants to remove suspended matter and chlorine
Nairobi 00100, Kenya disinfectation process to kill waterborne pathogens
e-mail: isaacwaweru2000@yahoo.co.uk (Marois-Fiset et al. 2013).
It has been found out that chlorine reacts with natural
J. C. Ngila
Department of Chemical Technology, University of Johannesburg, organic matter (NOM) forming undesirable chlorine
Doornfontein Campus, PO Box 17011, Doornfontein 2028 disinfectation by-products (DBPs) which are carcino-
Johannesburg, South Africa genic and endocrine-disrupting compounds (EDCs)
10 Page 2 of 18 Water Air Soil Pollut (2016) 227: 10

(Park et al. 2009). These secondary pollutants are a lived longer in water even though are less reactive
product of in situ reactions of relatively harmless reac- (Hall et al. 1992). As a result of such challenges, it led
tants such as NOM and dying pathogens with chlorine to the consideration of the development of an affordable
during the process of drinking water purification in material which can remove chlorine and chlorinated
water works. Studies by Morris et al. (1992) have linked organic compounds from water. This was achieved by
bladder cancers and rectal cancers in the USA to chlo- anchoring a zero-valent bimetal on a solid substrate. The
rinated drinking water. Such products have also been solid substrate material was non-biodegradable polysty-
found to be harmful and fatal to aquatic life and have rene sourced from waste. The study intended to exploit
been found in drinking water (Loeppky and Micheljda this abundant packing material which litters the envi-
1994). An example of one of the disinfectation products ronment especially in its foam form affecting the scenic
leads to the formation of N-nitrosodimethylamine beauty. It was expected that the use of that polystyrene
(NDMA) which is a known human carcinogen (Choi material for the intended purpose was environmentally
and Valetine 2003; Hyuckpark et al. 2009). friendly.
According to the U.S. Council of Environmental The degradation process was enabled through the
Quality, the cancer risk to people who drink chlorinated oxidation of the zero-valent iron, as it undergoes corro-
water is 93 % higher than those whose water does not sion to provide hydrogen and electrons for the dechlo-
contain chlorine (Dangers of Chlorine, http://www. rination reaction (Huang et al. 2009a, b), while the
com). In a study carried out in Belgium, it was second metal acts as a catalyst through the formation
reported that irritants such as trichloramines are of metal hydride which completes the dechlorination
released when chlorinated water interacts with organic process (Huang et al. 2009a, b).
body fluids such as sweat or urine (Dangers of Chlorine,
http://www.drweil.com). Another survey carried out in
Hartford, Connecticut, reported that women with breast 2 Material and Methods
cancer have 50 to 60 % higher levels of organochlorines
(chlorination by-products) in their breast tissue than 2.1 Chemicals and Reagents
women without breast cancer (Dangers of Chlorine,
http://www.drweil.com). Chlorinated water may have All the solutions were prepared in distilled water and the
an effect on lipid levels, such as an increase in both reagents were of analytical grade. Chloride standard
high-density lipoproteins (HDL) and low-density lipo- solutions were prepared by dissolving 0.1672 g of
proteins (LDL) (www.waterwarning.com). NaCl in 1000 ml of distilled water to form
Even with such reported risks associated with 100 g ml1 of chloride ions which were used to make
CDBPs, HIV-positive patients are encouraged and even 2 and 10 g ml1 calibration standards. A 5-M KNO3
provided with commercially available chlorine-based buffer solution was used to maintain a constant ionic
water treatment agents (sodium hypochlorite) to add to strength. The standard reference solutions for chloride
the already chlorinated water (www.waterguardinc. ion selective electrode calibrations were of analytical
com). This results in an increase of their chlorine grade from Sigma-Aldrich, a company in the UK.
uptake in the pretext of avoiding opportunistic
infections from contaminated water. Despite such 2.2 Instrumentation
dangers of chlorine disinfectation products (CDPs),
presenting a real and serious threat to our health, The chloride content in solution was determined by
chlorine is here to stay as there is no alternative of potential metric methods of analysis. The pH was mon-
doing away with chlorine any time in the near future. itored by the use of a pH meter (Jenway model number
The option therefore is to remove chlorine and 3505 made in the UK).The chloride ions were also
chlorinated by-products from water in our homes, at monitored by the use of ion selective electrode for
the point of use. chloride (Sentek model number 31824/001 made in
Available methods for the removal of excess chlorine the UK, together with an ion meter model number
and chlorinated organic compounds are expensive and 3345 made in the UK). The attached functional groups
not very effective (Hall et al. 1992). This is because the on the substrate-anchored zero-valent bimetals (ZVB)
removal methods tend to generate other species that catalyst were characterised using Fourier transform
Water Air Soil Pollut (2016) 227: 10 Page 3 of 18 10

infrared (FTIR) spectroscopy. An FTIR spectrophotom- then refluxed for 24 h. The resulting product was then
eter (FTIR-8400) in the range of 4000400 cm1 was filtered and washed with a mixture of concentrated HCl
used, in order to be able to give accurate information on and ethanol (45:50, v/v) followed by 2 M NaOH and then
the number of functional groups present in the nitrated, distilled water (Mwangi et al. 2010). The dried sample was
aminated and the metal-anchored polystyrene and those then analysed by ATR-FTIR spectroscopy.
that might be involved in the degradation processes. The
surface elemental presence of the substrate-anchored 2.3.3 Attachment of Zinc and Ferrous Ion
ZVB was confirmed using X-ray photoelectron spec- on the Polystyrene Substrate
troscopy (technical parameters of the TXRF spectrom-
eter S2 PICOFOX, Bruker). This method of analysis The metallic ions were anchored by physically mixing
also known as Electron Spectroscopy for Chemical 4.0 g of the modified polystyrene material with 3 M
Analysis (ESCA) is the most widely used surface anal- NiSO4, 3 M FeSO4 and 3 M ZnSO4 each separately, 3 M
ysis technique as it functions in a manner analogous to FeSO4 with either NiSO4 or 3 M ZnSO4 for the bimetal
SEM/EDS instruments that exploit an electron beam to and then in the ratio 1:1:1(12.0 ml) for the trimetal-
create SEM images of the analyte samples (Turner and anchored polystyrene (Mwangi et al. 2010). The con-
Al Jobory 1962; Kratos Axis Ultra X-ray Photoelectron centration of each of the respective metal ions was
Spectroscopy (XPS) system). 3.0 M.

2.3 Sample Preparation


2.3.4 Synthesis of Substrate-Anchored ZVB
2.3.1 Nitration of Polystyrene
The reduction of metal ions anchored on the polystyrene
was in situ using hydrazine. This was done by taking
Solid samples of polystyrene material, 6.0 g, were cut
50.0 g of the solid substrate, and to it, 50.0 ml of
into small pieces and activated at 60 C for 24 h. They
hydrazine hydrate was added. The mixture was heated
were placed in a 250-ml round-bottomed flask. To this
in a water bath at 70 C and the pH was maintained at a
sample, a 100-ml mixture of concentrated nitric acid and
value of 8.0 (Boudjahem et al. 2004a, b; Degen and
concentrated sulphuric acid in the ratio of 3:2 was added
Macek 1999; Li et al. 1999; Yang et al. 2004). The
and the mixture was refluxed for 24 h. The nitrated
reduction using hydrazine at basic pH results to harm-
material prepared was filtered, washed thoroughly with
less products of the metal-nitrogen gas which escapes
water, dried and then analysed by attenuated total re-
into the air water as shown in Eq. 1 (Huang et al. 2002).
flectance Fourier transform infrared (ATR-FTIR) spec-
troscopy. The aminated compound product was diazo- 2Ni2 N2 H4 4OH 2Ni N2 4H2 O 1
tized by cooling it in an ice bath (03 C); thereafter,
75 ml of 1 M NaNO2 was added followed by 100 ml of At pH values lower than 7.0, ammonia and water
1 M HCl. The mixture was stirred and tested with iodide become the end products as shown in Eq. 2 (Degen and
paper until the paper changed colour from white to Macek 1999; Li et al. 1999).
violet (Mwangi et al. 2010). The latter was then washed 3 N2 H4 N2 4NH3 2
with ice-cold water and coupled with ethylenediamine at
a temperature below 3 C for 24 h in an acetic acid Our reduction experiment was carried at basic pH,
media. The resulting brownish resin was filtered, and the resulting material was vacuum filtered using
washed with distilled water and dried in air for 24 h Buchner funnel and then ready for degradation
and then analysed by ATR-FTIR spectroscopy. experiments.

2.3.2 Reduction of the Nitrated Polystyrene 2.3.5 Characterisation of the Substrate-Anchored ZVB

The product obtained in Section 2.3.1 was reduced by FTIR Analysis FTIR analysis of the zero-valent bi-
placing 20.0 g in a 250-ml round-bottomed flask and metals and the trimetals was done to identify the func-
50.0 g granulated tin and 100 ml mixture of concentrated tional groups on the walls of the modified polystyrene
HCl and ethanol (45:50, v/v) were added. The mixture was and on the anchored ZVB substrate, responsible for the
10 Page 4 of 18 Water Air Soil Pollut (2016) 227: 10

chelating of the metal ions and reduction processes, re- solutions (0.10 g in 1000 ml) of each of 1,2-dichloro-
spectively. Potassium bromide (KBr) was used as the ethane, 2-chloro-2-methylpropane and 1-chlorobutane
background material in all the analysis. This was done by was prepared and adjusted to 6 g ml1 and added.
mixing 1.0 mg of the dried sample of each of nitrated The mixtures were equilibrated for 30 min. The mixture
polystyrene, reduced nitro polystyrene and metal-anchored was filtered and 5.0 ml of 5 M KNO3 ISAB added to
aminated polystyrene with 50.0 mg KBr (1:50), ground to maintain constant ionic strength, after which the chlo-
fine powder and pressed under vacuum to a pellet. The ride ions in the solution were analysed by potentiometric
pellet was analysed by an FTIR spectrophotometer (FTIR- methods.
8400) in the range of 4000400 cm1 (Naja et al. 2005).
This was done in order to give accurate information on the 2.4.3 Optimization of Reduction Time
number of functional groups present in the nitrated,
aminated and metal-anchored polystyrene and those that Aliquots of 25.0 ml model solutions of 6 g ml1 were
might be involved in the degradation processes. dispensed into a 100-ml plastic beaker containing ap-
proximately 0.1 g of each of the substrate bimetal cata-
X-ray Photoelectron Spectroscopy The surfaces of both lyst. The electrode potential of the model solutions was
metal complexed and ZVB substrate-anchored material monitored with time starting from 0 up to 60 min. The
were analysed by irradiating them separately with a chloride ions in the solution were analysed by potentio-
beam of X-rays and obtaining measurements of the metric methods.
kinetic energy and number of electrons that escape from
the surface simultaneously to determine the binding 2.4.4 Analysis of Environmental Water Samples
energy and their subsequent workfunction (Turner and
Al Jobory 1962). The XPS spectrum obtained is a plot Tap water and underground water samples were collect-
of the number of electrons detected as a function of ed and known concentrations of 2-chloro-2-
binding energy whose peaks are characteristic to each methylpropane spiked separately into each sample
element (Ray and Shard 2011). (25.0 ml). The respective mixtures were loaded onto a
100-ml plastic beaker containing 0.10 g of substrate-
2.4 Degradation of Chlorinated Compounds in Aqueous anchored ZVB, and the mixtures were equilibrated for
Media Using the ZVB 30 min. The mixture was filtered and 5.0 ml of 5 M
KNO3 ISAB added to maintain constant ionic strength,
2.4.1 Batch Reduction Experiments after which the chloride ions in the solution were
analysed by potentiometric methods.
Reduction (degradation) studies were carried out on a lab-
line mechanical stirrer using plastic beakers. The model
solutions, containing a known concentration of the chloride 3 Results and Discussion
ion, were adjusted to values between 0 and 10 g ml1.
Known weights (0.10 g) of the substrate bimetal catalyst 3.1 Synthesis of the Substrate
were added to each of the mixtures and then left to equil-
ibrate for 30 min allowing sufficient time for reduction. The The synthesis of the substrate-anchored ZVB is present-
mixture was filtered and 5.0 ml of 5 M KNO3 ionic ed in Scheme 1.
strength adjusting buffer (ISAB) added to maintain con- The resulting colour changed from brownish-green
stant ionic strength. The chloride ions in the mixture were to grey after reduction with hydrazine. The metal nano-
determined by the use of potentiometric methods. particles were immobilized on the polymer contributing
to the colour change. This was as observed by Mondal et
2.4.2 Optimization of the Substrate Bimetal Catalyst al. (2015) when they treated Cu(EDA)2 with hydrazine
Dosage and attributed to formation of zero valence copper. The
metal nanoparticles immobilized the polymer and is
Batches of substrate bimetal catalysts between 0.02 and evident as a grey colour (Yoon et al. 2003). The colour
0.12 g each were weighed and placed in a 100-ml plastic of the mixture was observed to change from brownish-
beaker. Thereafter, 25.0 ml of the chloride model green to grey due to the formation of metal nanoparticles
Water Air Soil Pollut (2016) 227: 10 Page 5 of 18 10

Scheme 1 The reaction process for the synthesis of the substrate-anchored ZVB

immobilized on the polymer. A similar observation was material. The resulting product was reduced using
reported by Mondale et al. (2015) as they reduced granulated tin and concentrated hydrochloric acid.
copper to a zero valence. The quantity of the metal will The resulting polystyrene material was characterised
depend on the amount of metal ions complexed prior to by FTIR and the resulting spectrum is presented in
the reduction. Fig. 2.
After the reduction of the nitro compound, the peaks
3.2 Characterisation observed at 1523.71, 1651.0 and 1226.0 cm1 disap-
peared due to the formation of an amine group. A strong
3.2.1 FTIR Characterisation of the Solid Substrate band at 3425.31 cm1 is attributed to either OH or NH
and Substrate-Anchored Metals groups (Stuart 1996). This band indicates the likelihood
of the presence of an amino (NH) group after the
Polystyrene material contains no functional groups reduction of the nitro functional group previously an-
capable for metal ion attachment. Attachment of chored on the polystyrene material (Stuart 1996). The
the metals was made possible by anchoring suit- band at 2935.5 cm1 was assigned to CH stretches,
able ligands to form complexes with metal ions of while the band at 1604.7 cm 1 was assigned to
interest within the structure of polystyrene. This stretching OH or N=C (Stuart 1996). New peaks such
modification process involved nitration of the ben- as 1647.0 and 2455.2 cm1 could be due to the NH2+
zene ring followed by a subsequent reduction to group. The peaks observed at 1527.5 and 1697.2 cm1
form an amino compound. The nitrated polysty- were assigned to the NH band, while the peak at
rene material was characterised by FTIR and the 3425.3 cm1 is due to the NH stretch. The peak ob-
resulting spectrum is presented in Fig. 1. served at 3109.0 cm1 could be due to the NH3+ group
The results show the presence of bands observed at (William 1991). The findings confirmed the reduction of
1523.7 and 1348.1 cm1 which could be due to asym- the presence of nitro groups within the polystyrene
metric and symmetric stretching of the nitro group, material to form amino functional groups which
respectively, in the ring structure which is characteris- were sites for metal attachment. The aminated
tic of a nitrogen-substituted ring (Sarma and Mishra polystyrene material was then treated with a mix-
2008). The bands at 850 cm1 and the regions between ture of metal solutions (Ni2+/Fe2+, Fe2+/Zn2 and
601.5 and 532.3 cm1 are due to various nitro substi- Zn2+/Ni2+/Fe2+) separately to form a complex of
tutions within the benzene rings Green and Harrison high stability between the metal and substrate
1970). A peak observed at 1600.8 cm1 was also (Chen et al. 1996). This is because during the
assigned to a nitro group attached to the ring interaction, a quasi-aromatic ring system forms a
(William 1991). Signals at 1226.6 and 1651.0 cm 1 dative bond with the metal (CNmetal) to make
could be due to N=O stretching (William 1991). The a ring system which is responsible for the stability
group could be a result of nitration of polystyrene due to ligand to metal charge electron transfer is
which is an electrophilic aromatic substitution reaction. formed (Chen et al. 1996; Krygowski et al. 2010;
The results confirm the nitration of the polystyrene Tas et al. 2006).
10 Page 6 of 18 Water Air Soil Pollut (2016) 227: 10

Fig. 1 FTIR spectrum of nitrated polystyrene

3.2.2 Reduction of Metal Ions in the Modified metal within the structure (William 1991). New bands in
Polystyrene the 518- and 617.2-cm1 region may probably be
due to the formation of metal-nitrogen bonds
The complex compounds formed between the sub- (Nakamoto 1978; Tas et al. 2006). The shift in
strate and the metals were reduced by treating with C=N predicts the concept of coordination of li-
hydrazine hydrate. The mixture was left to equili- gands through the nitrogen atoms (Nakamoto
brate for 24 h to form zero-valent metal-anchored 1978; Tas et al. 2006). This confirms the forma-
solid substrate. The resulting product was then tion of substrate-anchored zero-valent metal com-
analysed using ATR-FTIR spectroscopy. The plexes. The synthesis of iron, zinc or nickel zero-
resulting spectrum is shown in Fig. 3. valent particles at room temperature is possible as
After anchoring the metals, the strong bands at the standard reduction potential is more negative
3425.31, 2935.5, 1604.7, 1647, 2455.2, 1527.5, than 0.44 V (Yang et al. 2004). The reduction of
1697.2, 3425.3 and 3109 cm1 disappeared and new the metal ions was done using hydrazine hydrate.
bands were observed at 1110.9, 1190, 1384.8 and The reduction potential of hydrazine, N2H4, is a
1645.2 cm1. This may be due to the anchoring of the function of solution pH as shown in Eqs. 3 and 4

Fig. 2 FTIR spectrum of reduced nitrated (NH2) polystyrene material


Water Air Soil Pollut (2016) 227: 10 Page 7 of 18 10

Fig. 3 FTIR spectrum of anchored Fe/Zn on modified polystyrene

(Boudjahem et al. 2004a, b; Degen and Macek material appeared to be highly crystalline in nature.
1999; Li et al. 1999; Yang et al. 2004): The solid material was filtered and dried in air.

N2 4H 4eN2 H4 E 0:23 V 3
3.2.3 X-ray Photoelectron Spectroscopy
Characterisation of the Substrate-Anchored Metals

N2 4H2 O 4eN2 H4 4OH E 1:16 V The metal complexed and the ZVB substrate materials
4 were characterised by XPS and the resulting spectrum is
presented in Fig. 4.
The advantage of using hydrazine is that there is no The results show sharp peaks corresponding to
chance of the absence of the formation of metal subspe- each of the core level of elements of photoemis-
cies at other oxidation species (Boudjahem et al. 2004a, sion at its corresponding workfunction. This dem-
b). Despite hydrazine being highly toxic, it undergoes onstrates the evidence of the metals anchored on
self-oxidation and reduction at all pH conditions the material through complexation as shown in
resulting to the forming of nitrogen at basic pH or Fig. 4a. Upon reduction of the metals to zero
ammonia gas depending on the reduction during the valence, their presence, count rates and their re-
formation of zero-valent metal complexes as previously spective ratio of composition were not affected.
shown in Eqs. 5 and 6 (Degen and Macek 1999; Li et al. However, after reduction of the halogenated com-
1999; Huang et al. 2002). Reduction using hydrazine at pounds, the presence of the metal was evident as
basic pH results to harmless products of the metal- their corresponding peaks show, but the respective
nitrogen gas which escapes into the air-water. content of nickel was low because it was
sacrificed more than the other two during the
2Ni2 N2 H4 4OH 2Ni N2 4H2 O 5
degradation process as it had the lowest hydrogen
At pH values lower than 7.0, ammonia and water overpotential (Paknikar et al. 2008).
become the end products (Degen and Macek 1999; Li et
al. 1999). 3.3 Reduction Experiments
3 N2 H4 N2 4NH3 6
3.3.1 Batch Reduction Experiments
Our reduction experiment was carried at basic pH
and the resulting material was vacuum filtered using Reduction studies were carried out on a lab-line
Buchner funnel and was then ready for degradation mechanical stirrer using plastic beakers. The mod-
experiments. The metal-anchored solid substrate el solutions, containing a known concentration of
10 Page 8 of 18 Water Air Soil Pollut (2016) 227: 10

Fig. 4 Photoelectron energy spectra for iron, nickel and zinc anchored in substrate material. a Metal complexed material. b ZVB substrate
material. c Chlorine-degraded material

the chloride ion, were adjusted to values between 0 and 5.0 ml of 5 M potassium nitrate as an ionic strength
10 g ml1. Known weights (0.10 g) of the substrate adjusting buffer (ISAB) was added to maintain constant
bimetal catalyst were added to each of the mixtures and ionic strength. The chloride ions in the mixture were
then left to equilibrate for 10 min allowing sufficient determined by using a chloride ion selective electrode
time for reduction. The mixture was filtered, and to this, (ISE).
Water Air Soil Pollut (2016) 227: 10 Page 9 of 18 10

3.3.2 Optimization of Chloride Degradation


Parameters

Optimum degradation (reduction) parameters were in-


vestigated by varying one while maintaining the others
constant. The reduction temperature was set with a
thermostatted water bath shaker. The respective mix-
tures were allowed to equilibrate and removed from
the shaker at different time intervals. The substrate-
anchored ZVB were filtered off by suction and the
concentration of chloride ions in the filtrate was deter-
mined by potentiometric methods.

Degradation Kinetics The degradation rate is related to


the interaction of the reducing agent and the chlorinated
organic material (Demirbas et al. 2004). The degrada-
tion kinetics was studied so as to establish the number of
species involved in that process. It was done by taking
aliquots of 25 ml model solutions of 6 g ml1 which
were dispensed into 100 ml beaker containing approxi-
mately 0.1 g of each of the substrate bimetal catalyst.
The change in electrode potential of the model solutions
was monitored at predetermined time intervals of be-
tween 060 minutes. The relationship between electro-
chemical potentials and the concentrations of reactants
were done by exploiting the Gibbs free energy as shown
in the Nernstian equation (Atkins and Paula 2011).

n FE nFE RT lnQ 7

Where

E Electrochemical potential under standard state


conditions
n Number of electrons involved in the redox reaction Fig. 5 Rate of reduction of a 1-chlorobutane, b 1,2-dichloroeth-
F Faradays constant ane and c 2-methyl-2-chloropropane
Q Ration of the species in the redox reaction or
equilibrium constant
Equation 4 can therefore be re-written as shown in was sufficient to achieve maximum reduction as there
Eq. 8 below. was no further change observed in concentration with
time. The trimetal showed the highest chloride ion re-
E E  0:05916 logCl  8
lease (1.85 g) followed by Fe/Ni (1.6 g), while Fe/Zn
The results obtained from the experimental data (1.4 g) had the lowest concentration of chloride ions
showing the relationship between the logarithms of released.
chloride ion concentration against time were recorded From Fig. 4b, it was observed that in a contact time of
and presented graphically as shown in Fig. 5. 10 min, about 1.8 g of chloride ions was released and
From Fig. 4a, it was observed that in a contact time of more than 90 % of the halide had degraded; thus, 10 min
10 min, about 1.8 g of chloride ions was released and was sufficient to achieve maximum reduction as there
more than 90 % of the halide had degraded; thus, 10 min was no further change observed in concentration with
10 Page 10 of 18 Water Air Soil Pollut (2016) 227: 10

time. The trimetal showed the highest chloride ion re- The experimental data was treated with pseudo first-
lease (1.8 g) followed by Fe/Ni (1.6 g), while Fe/Zn order and second-order kinetic model equations
(1.4 g) had the lowest concentration of chloride ions (Lagergren 1898; Ho et al. 2000). The first-order and
released. second-order kinetic models are expressed as follows,
From Fig. 4c, it was observed that in a contact time of respectively:
10 min, about 1.8 g of chloride ions was released and
lnC Kt A 9
more than 90 % of the halide had degraded; thus, 10 min
was sufficient to achieve maximum reduction as there
was no further change observed in concentration with
1
time. The trimetal showed the highest chloride ion re- Kt A 10
lease (1.83 g) followed by Fe/Ni (1.59 g), while Fe/ C
Zn (1.39 g) had the lowest concentration of chloride Where
ions released.
The general observation made was that the rate of C Log of concentration of the chloride ions
reduction of chlorine and chlorinated organic com- A y-intercept
pounds is related to the efficiency of the substrate K Slope
bimetal catalyst and activity of the halides and there- t Time in minutes
fore controls the residence time of the oxidant at the The degradation of 1-chlorobutane was treated with
solidsolution interface (Demirbasa et al. 2004). the Lagergren (1898) first-order kinetic model and the
Despite some chloride ions being registered at results obtained are presented in Fig. 6.
0 min contact time, the degradation rate was fast The results show a linear relationship with a slope of
since 90 % of the reduction occurred within 10 min 0.0546 mol min1 of the chloride ions with a linear
after which a steady-state reduction was realised regression of 0.997. The Nernst slope obtained in this
(Fig. 4ac). The initial rapid degradation rate (within experiment deviated slightly with the expected theoret-
the first 10 min) is due to reduction of the halogen ical value for a one-electron transfer (Pace and
by the immobilized ZVBM (Khani 2006). This was Stankovich 1987; Mwangi et al. 2010).
followed by a degradation lower rate contributed by The degradation of 1-chlorobutane was treated
the decreasing zero-valent metal content in the sub- with the Lagergren (1898) second-order kinetic
strate. The surface reactive sites responsible for the model and the results obtained are presented in
degradation get degraded upon contact with chlorine Fig. 7.
containing chlorinated organic material resulting to a The results show a linear relationship with a slope of
passivating layer affecting the kinetics and product 0.0837 mol min1 of the chloride ions with a linear
formation (Tee et al. 2009). regression of 0.964. Based on the linear regression
It was observed that a contact time of 20 min was values of 0.997 and 0.964 for the same halides, it im-
sufficient to achieve maximum reduction as there was plies that the reduction reaction was a pseudo first order.
no further change observed in concentration with time. The results of all the other degradation processes
The results show that the amount of chloride ions re- were recorded in a tabular form, showing the rate con-
leased by the ZVB substrate increased with increasing stant and regression constants for each. It is presented in
time of equilibration and reached a plateau value at Table 1.
about 20 min for all the three halides and with the three The general observation made from Table 1 was that
different ZVB catalysts. Since 10 min was sufficient the pseudo first-order equation fitted the experimental
interaction time for the removal of the chlorine in the data on the degradation process of 1,2-dichloroethane,
synthesized solutions, subsequent reactions were carried 2-chloro-2-methylpropane and 1-chlorobutane. Figure 5
out at a contact time of 30 min. From the experimental indicates that the pseudo first-order equation provided a
data, it was found out that the material was therefore near perfect match between the theoretical and the ex-
suitable for remediation of water having organic chlori- perimental values. The pseudo first-order equation rate
nated compounds at a point of use. From the kinetic constant K for reduction of 1,2-dichloroethane, 2-
studies, the data was used to determine the degradation chloro-2-methylpropane and 1-chlorobutane was
order. 4.679, 5.208 and 5.208 g l1 min1, respectively. The
Water Air Soil Pollut (2016) 227: 10 Page 11 of 18 10

Fig. 6 Plot of lnC against time


for the reduction of 1-
chlorobutane

reduction pseudo first-order equation was developed trimetal showed the highest reduction capacity followed
based on the assumption that the rate-limiting step by Fe/Ni, and Fe/Zn had the least.
may be chemisorption. This suggests that the reduction It is observed that the pseudo first-order reaction rate
was as a result of the ZVB substrate as reported by constants for the Fe/Zn, Fe/Ni bimetals and the trimetal
Babalola et al. (2009). were 2.370.01 (R2 =0.9980.001), 3.550.01 (R2 =
Thus, the interaction between the halide and ZVB 0.9890.001) and 3.720.01 (R2 =0.9920.001), re-
substrate is the rate-determining step (Herrero et al. spectively. The rates in our study have the same order
2008). The reactions followed first-order kinetics, show- of magnitude with the reported result in Xu et al. (2005)
ing that the degradation process was not dependent on and three times higher than those in Tee et al. (2005) and
intermediates or other species in solution. Meyer et al. (2004). The difference in the rate constants
A similar treatment was done for the degradation of the halide degradation in this study from those re-
using bi- and trimetal substrate-anchored materials. corded in the literature could be caused by different
The results were recorded as shown in Table 2. factors. These include the synthesis method and the
The results show that Fe/Ni gave better results with a use of membrane systems with different polymeric
slope of 0.05916 V which agrees with the theoretical properties that might affect the transport of halides to
slope for one exchangeable electron. The slope for the the particles. The lower reaction kinetic with Zn content
Fe/Zn ZVB was 0.05734 V which is close to the can be explained by zincs competition with iron that
theoretical value for one exchangeable electron and thus will hinder the electrochemical process of the zero-
can be used in water remediation at the point of use. This valent iron that generates electrons and assists in the
is because the two metals are non-toxic at fairly high production of hydrogen needed for the reduction of the
concentration (Matheson and Tratnyek 1994). The halide (Park et al. 2009; Burke et al. 1991).

Fig. 7 Pseudo second-order


graph for the concentration of
chloride ions
10 Page 12 of 18 Water Air Soil Pollut (2016) 227: 10

Table 1 Summary of the regression values for the halides

Halide Slope First order Second order Comment


R2 R2

1,2-Dichloroethane 0.05960.0001 0.9960.001 0.9580.001 First order


2-Chloro-2-methylpropane 0.04600.0001 0.9970.001 0.9640.001 First order
1-Chlorobutane 0.05460.0001 0.9970.001 0.9790.001 First order

Determination of Chloride Ions The potential differ- difference and the concentration of the degraded chlori-
ences from the degradation process (30 min) using the nated compounds. The levels of chloride ions from the
substrate-anchored bimetal and trimetal for the degrada- degraded chlorinated organic compounds were therefore
tion on 1,2-dichloroethane were recorded. The relation- determined by this method.
ship between the potential difference and the natural The degradation of the three halides under study was
logarithm of concentration of chloride ions in the solu- carried out. The reduction potentials from the degrada-
tion was recorded graphically as shown in Fig. 8. tion of different concentrations of the synthetic solution
The results show a linear relationship with a slope of the dissolved halides were recorded. From that, the
of 0.05734 V mol1 of the chloride ion with a concentrations of the evolved chlorides were evaluated
linear regression of 0.997 with the degradation with with the help of the Nernstian equation. The results
Fe/Zn bimetal material. The Nernst slope of obtained were recorded in tabular form as presented in
0.05734 V compared well with other studies mon- Table 3.
itored in the presence of organic compounds for a From the data in Table 3, it was observed that the
one-electron transfer (Pace and Stankovich 1987; electrode potential decreased with the increase in the
Mwangi et al. 2010). concentration of the halide. The trimetal showed the
In another degradation experiment of chloride ions highest decrease in electrode potential followed by Fe/
in synthetic solutions by zero-valent iron/nickel Ni, while Fe/Zn had the lowest electrode potential de-
substrate-anchored bimetals, the results show a linear crease. From the data in Table 3, graphical representa-
relationship with a slope of 0.05916 V mol1 of the tions of the effect of halide concentrations were recorded
chloride ion with a linear regression of 0.989. The as shown in Fig. 9.
Nernst slope obtained in this experiment is the ex- The results show that the concentration of chlo-
pected theoretical value for a one-electron transfer ride ions increased with the increase of the halide
(Pace and Stankovich 1987; Mwangi et al. 2010). In concentration. This implied that the chloride ions
the degradation process with the valent iron/zinc/ getting into the solution were from the halide. This
nickel substrate-anchored trimetal, it was observed is attributed to the fact that concentration is the
that the linear relationship had a slope of driving force for the halide to interact with the
0.05899 V mol1 of the chloride ion with a linear available reduction sites (Ilhan et al. 2004). After
regression of 0.992. The slope is within the expected a concentration of 5 g l1 of halide concentration,
theoretical value for a one-electron transfer (Pace and a plateau was observed implying that the degrada-
Stankovich 1987; Mwangi et al. 2010). tion process was no longer proportional to the
From the information obtained, it was confirmed that halide concentration. At that point, the degrading
there was a relationship between the measured potential agent is said to be saturated (Benhima et al. 2008).

Table 2 Table of kinetics of the reduction process

ZVB K (mg l1 h1) Slope (mV) R2 Reaction order

Fe/Zn 2.370.01 57.340.01 0.9980.001 First-order


Fe/Ni 3.550.01 59.160.01 0.9990.001 First-order
Fe/Zn/Ni 3.720.01 58.990.01 0.9920.001 First-order
Water Air Soil Pollut (2016) 227: 10 Page 13 of 18 10

Fig. 8 Relationship between the


potential difference and the ln of
halide concentration
10 Page 14 of 18 Water Air Soil Pollut (2016) 227: 10

Table 3 Reduction potentials of three halides by substrate-anchored bimetals and trimetal

Conc (g ml1) 1,2-Dichloroethane (mV) 2-Chloro-2-methylpropane (mV) 1-Chlorobutane (mV)

Fe/Ni Fe/Zn Fe/Zn/Ni Fe/Ni Fe/Zn Fe/Zn/Ni Fe/Ni Fe/Zn Fe/Zn/Ni

0 158.3 158.3 158.3 185.6 158.3 158.3 158.3 158.3 185.6


2 190.1 190.1 190.2 250.6 237.9 250.9 248.1 230.1 241.2
4 243.2 238.1 242.1 261.2 248.4 260.9 259.9 241.6 250.6
6 269.2 258.7 266.9 272.3 259.1 271.1 266.2 248.9 256.5
8 275.3 273.3 276.1 282.3 267.3 279.2 276.1 254.3 263.5
10 290.1 280.9 289.9 289.4 278.2 284.7 279.2 268.3 270.2

Effect of Reduction with ZVB Substrate Dosage The fact that the substrated degradation capacity was
effect of the mass of the ZVB on the degradation process surpassed by that concentration of the halides. At a mass
was studied. This was done using 25-ml model solutions of 0.1 g of the ZVB substrate material, 5.4 g of the
of the three halides each of the concentration of halide was degraded. This gave a degradation capacity
10 g ml1 using a 100-ml plastic beaker. The results of the halide to be 54 g g1 of the ZVB.
obtained after 30 min of degradation period were pre- From Table 3, it was found that the concentration of
sented graphically as shown in Fig. 10. chloride ion generation increased in the order of 1,2-
It was observed that there was an increase in the dichloroethane > 2-chloro-2-methylpropane > 1-
concentration of the chloride ions released into the so- chlorobutane. This may be due to the high polarizing
lution with increase in the mass of bimetals and trimetal power associated with strong carbon cations in the case
used. The results show that the reduction of the three of 2-chloro-2-methylpropane and 1-chlorobutane,
halides increased with the increase in substrate- whereas 1,2-dichloroethane is attached to two chloride
anchored ZVB dosage. This could be because the re- atoms (Eric et al. 2004).
duction process was due to the stoichiometric interac- This showed that the bimetallic system, based on the
tion ratio between the halide and ZVB substrate as degradation process with Fe/Zn-anchored substrate ma-
observed by Puranik et al. (1997). At higher substrate- terial, provided a satisfactory result for the degradation
anchored ZVB to halide concentration ratios, there is a of chlorinated organic compounds and can be used for
very fast superficial adsorption onto the substrate- their removal at the point of use. This is in agreement as
anchored ZVB surface that produces a lower halide reported by other researchers such as Odziemkowski et
concentration in the solution than when the substrate- al. (2000), Wang et al. (1997) and Campbell (1998) who
anchored ZVB to halide concentration ratio is lower. carried different organic chlorinated degradation exper-
This is because a fixed mass of substrate-anchored ZVB iments. From that observation, degradation of environ-
can only reduce a certain amount of the halide (Davila- mental sample was done using the Fe/Zn-anchored
Jimenez et al. 2003; Fourest et al. 1992). The increase
was observed up to the mass of 0.1 g ZVB after which a
plateau was observed. This could be attributed to the

Fig. 9 The effect of initial halide concentration for determination Fig. 10 The effect of variation of the mass of Fe/Zn substrate on
of reduction capacity the reduction of the halides
Water Air Soil Pollut (2016) 227: 10 Page 15 of 18 10

0.001) and 3.720.01 (R2 =0.9920.001), respective-


ly. The rate of reduction was very fast as more than 90 %
of the halides were reduced in less than 10 min. It was
observed that the zero-valent metals in the solid sub-
strate oxidized with time and could be regenerated by
running hydrazine hydrate to reduce them to zero va-
lence. The degradation kinetics was found to be of first
order hence suitable for application with no other cata-
lysts. Results of this work illustrate the potential appli-
cation of zero-valent metal-anchored substrate material
Fig. 11 Percent recovery of the halide from an environmental
water sample for the removal of chlorine and chlorinated organic
compounds from water at the point of use. In general,
substrate material. The results obtained are presented in the study offers a solution to addressing the problem of
Fig. 11. water pollution through treatment by removing chlori-
The results show that the highest amounts of chloride nated organic compounds.
ions were recorded on the waters from the shallow well.
Acknowledgments The authors would wish to thank their col-
This is because even if it was doused with the required leagues of Kenyatta University Chemistry Department postgradu-
amount of chloride ions, there is a likelihood of having a ates research group for their support, the staff of the Department
high bacterial load and organic matter contributing to a of Chemistry, Kenyatta University for guidance and the Teachers
higher chlorine disinfectation product. The same could Service Commission for the study leave to undertake the postgrad-
uate course.
be explained for the Kiamumbi waters which is within
the proximity of the sample site and is sourced from a
river surrounded by greenhouses. Nairobi water record-
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