Experiment 8: Determination of Lead using Anodic Stripping Voltammetry

Chem 127.1 MEJ

2012-24633

September 21, 2015

I.
ABSTRACT
Lead contamination is a major global problem as it can lead to diseases such as anorexia, malaise, vomiting,
convulsions, permanent brain damage and anemia. Hence, an easy method to accurately determine Pb concentration in
drinking water samples is important. Square Wave Anodic Stripping Voltammetry offers several advantages from other
electrochemical techniques due to its rapid determination and higher sensitivity. Square Wave Anodic Stripping
Voltammetry was used to determine Pb concentration in the water sample obtained from the College of Arts and
Sciences, UP Manila drinking fountain. The sharp peaks obtained in the voltammogram indicate that the setups sensitivity
to lead. The linear equation obtained from standard addition analysis is y=205322x + 0.3697 (R = 0.99987). From this
equation, the initial current prior to standard addition was determined to be 0.3697 mA the concentration of Pb, which is
equal to the value of the x intercept, was found to be 1.79736 ppb. This signifies that the water sample is within the
acceptable range for lead and is safe for human consumption.
_________________________________________________________________________________________________
Keywords: anodic stripping voltammetry, square wave voltammetry, electrodes, deposition, lead, standard addition
II.

INTRODUCTION

III.
IV.
Although not as common, one of
the major global problems is lead contamination.
Metals, such as lead have the tendency to
accumulate in vital organs, due to their nonbiodegradability. Acute lead poisoning is
causative of anorexia, malaise, vomiting,
convulsions and permanent brain damage while
chronic lead poisoning can cause weight loss,
weakness and anemia. Toxic chemicals and
metals are sometimes incorporated into drinking
water and various food chains by leeching from
solder used to join copper pipes, lead from point
in older buildings and dust/soil contaminated
with tetraethyl-lead (Bard, 2001).
V.
The EPA, with two levels of
protection has set drinking water standards.
Although the maximum contaminant level goal is
zero, the final rule establishes an action level at
15 ppb. That means that water with more than
15 ppb lead is not safe to drink.
VI.
Despite a number of sensitive
and reliable techniques for trace analysis such
as atomic flame spectrometry and spark
spectroscopy, the high cost of instrumentation,
extensive sample preparation and limited
selectivity reduces the efficacy of these
techniques in sample matrixes such as water.
Stripping voltammetry is a useful technique for

Chem 127.1 Expt 8

2012-24633

trace analysis due to its relative ease, costeffectiveness and sensitivity. A minimal sample
of the water to be tested would be able to
identify and quantify the trace components
selectively and sensitively from 10-5 to 10-9 M.
Stripping analysis is the most sensitive electro
analytical technique currently available. Anodic
stripping voltammetry is a type of stripping
voltammetry often used for trace level
determination of metals such as lead cadmium,
clinical and industrial samples. It can detect and
analyze very low levels of several heavy metals
simultaneously in the same ppm or even ppb
range. Anodic stripping voltammetry works by
electroplating the desired metal in solution on an
electrode. The metals on the electrode are then
stripped off, generating a measurable current
proportional to the amount of metal being
stripped off. Since the potential of the removed
metal is characteristic, the metal can be
identified and quantified (Rutyna, 2014).
VII.
Different sweep types can be
used for anodic stripping voltammetry. The
experiment used square wave voltammetry
wherein the obtained potential waveform
consists of a square wave of constant amplitude
superimposed on a staircase waveform. After
every half cycle, the current is measured. The
current measured on the reverse half-cycle is
subtracted from the current measured on the

Page 1

X.

forward half cycle. The obtained current

difference is displayed as a function of the
applied potential (ASA Analytics, 2015). Square
wave voltammetry is often used to increase
analysis time and decrease detection limit. It is
faster and more sensitive compared to the other
alternatives, linear and differential pulse sweep.
(Brett, 1994) Using anodic stripping voltammetryXIX.
with square wave voltammetry as its sweep type
offers a faster determination step, allows testing
even with oxygen present in the solution, and
offers higher sensitivity (Brett, 1994)
VIII.
The experiment aimed to use
anodic stripping voltammetry with square wave
voltammetry as its sweep type and determined
the corresponding lead concentration from a
water sample obtained from the UP Manilas
CAS drinking fountain.
IX.
METHODOLOGY

XI.
XII.

Two mL of water from

the CAS drinking fountain was added
with 5 mL of 1.0 M acetate buffer, 0.200
mL of 100 ppm Bi. The sample was
maintained at pH 4.0-4.5 using NaOH
and/or NO3. Appropriate potentiostat
leads were connected to the electrodes
and submerged in the sample produced.
1 cm of the pencil graphite was
submerged in the sample, maintaining
the position of the electrodes throughout
the
analysis.
Anodic
stripping
voltammetry was done with the following
parameters:
XIII.
Conditioning step: E = +500
mV, t = 20 s
XIV.
Deposition step, E = -1000 mV,
t = 120 s
XV.
Equilibration or rest step, E =
-1000 mV, t=10 s
XVI.
Stripping step, Efinal = +500 mV,
Estep = 5 mV, pulse amplitude = 25 mV, v
= 20 Hz
XVII.
0.1 mL of the 2.5 ppm standard
was then added to the solution. ASV was
repeated using the same parameters. Standard
additions were repeated until the desired

Chem 127.1 Expt 8

2012-24633

number of additions was complete. To ensure

that no lead signal arose from reagent or
apparatus contamination, the blank sample was
analyzed before each new addition. The
accuracy of the methods was then verified by
analyzing the results with a control sample.

XVIII.
RESULTS AND DISCUSSION

XX.
XXI.
Anodic Stripping Voltammetry with
Square Wave Voltammetry as a sweep type is
widely used for individual and simultaneous
determination of trace amounts of heavy metals
such as lead in environmental samples.
XXII.
Pulse voltammetric techniques are able
to discriminate against charging current; hence
these techniques are more sensitive to oxidation
and reduction currents than conventional
voltammetry. Square wave voltammetry is
commonly used as a voltammetric technique as
it can perform and experiment much faster than
normal and differential pulse techniques. Square
wave voltammetry typically employ scan rates
up to 1V/sec or faster, producing much faster
determinations. The rapid scan rates allow the
entire voltammogram to be recorded on a single
mercury drop. A symmetrical wave is
superimposed on a staircase waveform where
the forward pulse of the square wave is
coincident
with
the
staircase
step.
(Ramaley,1987).
XXIII.
XXIV.
Stripping voltammetry can be either
anodic or cathodic. Anodic stripping voltammetry
has a working electrode that behaves as a
cathode during the deposition step and as an
anode during the stripping step. For cathodic
stripping voltammetry, the working electrode
behaves as an anode during the deposition step
and a cathode during the stripping step (Skoog
2007).
XXV.
XXVI.
Anodic Stripping Voltammetry
involves
electrochemical
oxidation
of
preconcentrated analyte and use of three
electrodes, working, auxiliary and reference.
Two types of mercury electrodes are commonly
used, the Hanging Drop Electrode (HMDE) and

Page 2

the Thin Mercury Film Electrode (TMFE) which

is often formed in the preconcentration step by
deposition of small amounts of mercury on the
carbon electrode. Bismuth Thin Film Electrodes
(BTFE) are used as an alternative to Thin
Mercury Film Electrodes due to its decreased
toxicity and comparable activity. BTFE has a
higher surface-area to volume ration than
HDME, leading to a higher analyte concentration
for a given time. Also, the bismuth film is
inherently more stable than the mercury drop.
Therefore, the stirring during the deposition step
is much faster with BTFE. Hence, deposition
time is much shorter with BTFE. However,
HMDE is more reproducible than BTFE because
the structure of the bismuth layer on BTFE is
very dependent on the surface of the carbon
electrode, hence is not easily reproducible.
XXVII.
XXVIII.
Anodic Stripping Voltammetry has three
steps. The first step is the electrodeposition
step, which involves the electrochemical
deposition of the metal of interest to the surface
of the working electrode, which is usually a
mercury film electrode or a hanging mercurydrop electrode. To achieve a fairly concentrated
amalgam, proper conditions such as a short time
for electrolysis, stirring, and the proper potential
are essential. The concentration of the metal on
the mercury film is dependent on the
concentration of the metal present in the
solution. The deposition step allows stripping
methods to detect analytes at very low
concentrations (Ramaley, 1987).
XXIX.
The equation for the first step is:
Mn+ + ne- + Hg -> M(Hg)
XXX.
XXXI.
The concentration of the
reduced metal is
XXXII.
C= it/nFV
XXXIII.
Where:
XXXIV.
i=limiting
current
for
the
reduction or deposition of the metal
XXXV.
t=deposition time
XXXVI.
n=number of moles of electrons
transferred in the half reaction
XXXVII.
F=Faradays constant
XXXVIII.
V =volume of the electrode

Chem 127.1 Expt 8

2012-24633

XXXIX.
XL.
The applied potential is maintained to be
at -0.4V compared to the standard potential of
the ion with the lowest reduction potential.
Stirring of the solution was facilitated because
the deposition step is controlled by masstransport, specifically convection through
stirring. Thus, stirring effectively reduces
deposition time and the speed of the deposition
can be increased by increasing solution stirring.
XLI.
XLII.
The second step is the rest period. After
a predetermined amount of time, the stirring is
discontinued. The solution is allowed quiescence
to
reach
a
uniform
metal
amalgam
concentration. The rest period is often 15-30
seconds of unchanged applied potential,
ensuring no reoxidation of the metal by oxygen.
The electrodeposition current decreases during
the rest period. (Paneli, 1993).
XLIII.
XLIV.
The third step is the stripping
step. During this step, the electrode potential is
swept to very high, positive potentials which
induces the oxidation of the metal in the mercury
electrode. When the standard metal ion redox
potential is reached by the applied potential on
the working electrode, the metal is stripped from
the amalgam. This occurs due to the oxidation of
the metal under conditions of diffusion control
using a voltammetric method:
XLV.
M (Hg) = Mn+ + ne
XLVI.
XLVII.

Page 3

XLVIII.

Figure 1. AS Voltammogram of
sample from drinking fountain.

XLIX.
LXVI.
=1.710 ppb
L.
Based on the voltammograms,
LXVII.
LXVIII.
CONCLUSION
AND
the corresponding oxidation of Pb is shown from
RECOMMENDATIONS
its peak. The peak height is proportional to the
LXIX.
concentration of metals in solution. Hence, prior
LXX.
Anodic stripping voltammetry coupled
to sample analysis, calibration must be
with
square
wave voltammetry is effective in
accomplished.
determining
trace
metals such as lead in water
LI.
samples.
It
has
high sensitivity, stability,
LII.
For the experiment, four mL of
simplicity and suitability that allow accurate
water from the UPM CAS drinking fountain were
analyte determination even at very low
analyzed for lead determination. 100 ppm Bi in
concentrations. Experimental analysis showed
25% HNO3 was added to the sample because
that the drinking fountain water has a lead
lead deposits on bismuth, producing a
concentration of 1.79736 ppb, which is below
measurable signal. A pH of 4-4.5 was
the 15 ppb point of action concentration. Hence,
maintained to dissolve the bismuth, increasing
the water from the UPM CAS drinking fountain is
the sensitivity of the working electrode (Wang,
safe for human consumption.
et. al., 2000)
LXXI.
LIII.
LXXII.
The protocol must be followed
LIV.
The peak heights observed
to the letter: pH must be properly maintained,
indicates the setups sensitivity to lead. These
stirring must be effective, dissolved oxygen
were manually measured and plotted against the
should be lessened and the set-up must be
corresponding amount of Pb added to the
maintained all throughout the experiment for
sample. Table 1 of the appendix summarizes the
accurate determination of lead.
peak heights for the voltammogram and
LXXIII.
standard addition.
LXXIV.
LV.
The standard addition plot was
LXXV.
VI. REFERENCES
obtained by plotting x vs y, as shown in Figure 2
LXXVI.
of the appendix.
LXXVII.
Barn-Jaimez,
J., Joya, M. R., & Barba-Ortega,
LVI.
J. (2013). Anodic stripping voltammetry
LVII.
As observed from the graph in
ASV for determination of heavy metals.
the appendix, the linear equation is y = 205322x
In Journal of Physics: Conference
+ 0.3697 (R = 0.99953). From the previously
derived equation for standard addition, the LXXVIII.
y
intercept 0.3697 has the same value with theLXXIX. Bott, A. (n.d.). Voltammetric Determination of
current of the sample prior to standard addition.
Trace Concentrations of Metals in the
Meanwhile, the concentration of Pb is equal to
Environment. Retrieved September 4,
the x-intercept value. When y=0, Pb
2015,
from
concnetration was found to be 1.910 ppb.
http://currentseparations.com/issues/14LVIII.
1/cs14-1d.pdf
LIX.
Calculations:
LXXX.
LX.
(Ix +s) (Vx+Vs)/Vx = ((Ix +s)/Cx)LXXXI. Mirceski, V., Komorsky-Lovric, S, & Lovric, M.
(CsVs/Vx) +Ix+s
(2007).
Square-wave
voltammetry:
LXI.
y
m
Theory and application.
Springer
x
b
Science & Business Media.
LXII.
LXXXII. me
LXIII.
b= Ix +s =0.3697
LXXXIII. United Stated Environmental Protection Agency.
LXIV.
m= (Ix+s)/Cx = 205322
(n.d.). Basic Information about Lead in
LXV.
Cx= 0.3697/205322

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2012-24633

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Drinking Water. (n.d.). Retrieved

September 7, 2015.

LXXXIV.
LXXXV.

LXXXVI.
LXXXVII.

LXXXVIII.
XC.
XCI.
XCII.
XCIII.
XCIV.
XCV.
XCVI.
XCVII.
XCVIII.
XCIX.
C.
CI.
CII.

CIII.
CIV.
CV.
Skoog, D.A., Holler, F.J., Crouch, S. R. (2007). CVI.
Principles of Instrumental Analysis, 6th CVII.
ed. USA: Thomson Brooks/Cole
CVIII.
CIX.
Wang, J., Lu, J., Hocevar, S. B., Farias, P. A., &
CX.
Ogorevc, B. (2000). Bismuth-coated CXI.
carbon electrodes for anodic stripping CXII.
voltammetry. Analytical
CXIII.
CXIV.
LXXXIX.
CXV.
CXVI.
CXVII.

CXVIII.
CXIX.
CXX.
CXXI.
CXXII.
CXXIII.
CXXIV.
CXXV.
CXXVI.
CXXVII.
CXXVIII.
CXXIX.
CXXX.

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CXXXI.

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