Hydrometallurgy 2003 – Fifth International Conference in Honor of Professor Ian Ritchie –

Volume 1: Leaching and Solution Purification

Edited by C.A. Young, A.M. Alfantazi, C.G. Anderson, D.B. Dreisinger, B. Harris and A. James
TMS (The Minerals, Metals & Materials Society), 2003

SURFACE-ENHANCED RAMAN SPECTROSCOPY OF GOLD

DISSOLUION IN CYANIDE: SYSTEM PURITY EFFECTS
K. Watling, G. A. Hope & R. Woods1
1
Griffith University and CRC for microTechnology
Kessels Rd., Nathan, 4111, Queensland, Australia.
k.watling@sct.gu.edu.au

Abstract

Vibrational spectra of surface and solution compounds formed during cyclic voltammetry of a
gold electrode in a deoxygenated 0.01 mol dm-3 NaCN solution have been examined using
surface-enhanced Raman scattering (SERS) spectroscopy. The presence of cyanide at the
electrode surface was indicated by Raman bands characteristic of the carbon-nitrogen stretch,
νCN.. Chemisorption of cyanide on the gold surface was evidenced by the presence of
vibrational modes due to gold-carbon stretching, νAuC, and gold-carbon-nitrogen bending,
δAuCN. Prior to the disappearance of the surface cyanide stretch band, a limiting value of the
νCN was obtained, the same as the value reported for adsorbed cyanide. Effects upon the
voltammetry and vibrational modes of surface species due to additions of silver and lead to the
gold-cyanide system have been observed.

Introduction

The leaching of gold in dilute aerated cyanide solutions has been the basis of gold extraction for
the past century, but despite the extensive number of studies of the electrochemistry, kinetics
and mechanism of the reaction, acceptable agreement has not been reached [1]. Discrepancies
between the cyanidation rate reported by Kudryk & Kellogg and those subsequently obtained
by various other authors have been particularly troublesome. Jeffrey and Ritchie have recently
revisited this ongoing quandary, and have proposed that the various levels of purity of the gold-
cyanide systems investigated may be the cause of disagreement, particularly with respect to
lead contamination in AR solutions and to the silver content of the gold [1, 3] Their premise is
based upon observations that impurities such as lead, thallium, bismuth and mercury can
accelerate the cyanidation process, leading to an increased rate of gold leaching [4, 5].

Jeffrey and Ritchie used their rotating electrochemical quartz crystal microbalance (REQCM) to
examine the electrochemistry and cyanidation rates of the process in high purity vs AR grade
cyanide solutions, and examined additions of silver and lead impurity ions [1, 3]. They contend
that impurities found in AR grade cyanide can introduce up to 5 ppb lead and 1.5 ppm chloride
to the leach solution at cyanide concentrations of 0.02 mol dm-3, and that such trace
concentrations have been found to accelerate the cyanidation process. Their high purity
cyanide solutions were prepared by bubbling hydrogen cyanide gas directly into a sodium
hydroxide solution to avoid lead contamination from AR grade cyanide. It was shown that, in
the case of AR cyanide, rapid gold dissolution was evident due to a loss of mass, while in
ultrapure cyanide a slight mass increase was observed, indicating passivation of the leaching
process by an adsorbed layer. Jeffrey & Ritchie suggest that this mass increase is due to a
polymeric gold(I) cyanide, previously proposed by Nicol [6], and that the chain ends of this
polymer layer are attacked by cyanide to form the dicyanoaurate ion, the stable product of gold

49
dissolution in cyanide [1]. The authors suggested that the incorporation of impurities such as
lead into the gold surface provides a termination point for the cyanide polymer, increasing the
number of chain ends available for dissolution. Despite the evidence provided by the REQCM,
the exact molecular nature of the adsorbed cyanide layer was not established. An ancillary
technique is therefore required to determine absolutely the composition and bonding
characteristics of the passivating adlayer.

The SERS technique enables the observation of vibrational modes of compounds adsorbed
upon or in close proximity to an appropriately activated gold, silver or copper surface [7].
SERS activation procedures involve the formation of nanoparticles or surfaces with suitably
spaced gratings. Resonance of the applied radiation with plasmon modes in the nanospheres or
gratings causes a strong local electromagnetic field to emanate from the metal surface [8].
Molecules in close proximity to this field or adsorbed to the metal surface undergo an increase
in the intensity of Raman scattering of the order of 10 [6] to 10 [14] times that of normal [7].
Cyanide is a strong Raman scatterer, therefore the technique of SERS is well suited to the study
of cyanide interaction with a gold surface.

The technique of rapidly acquiring SERS spectra during a voltammetric ramp was pioneered in
1979 by Dornhaus et al, [9] who adapted a CCD optical multichannel analyser and computer-
based collection system to a conventional Raman spectrometer. Prior to this, or without the
benefit of such a rapid collection system, electrochemical SERS data was acquired in a static
mode, with the electrode held at a set potential during the collection of spectral data. Current
Raman spectrometer technology features sensitive computer interfaced CCD collection devices,
which, when coupled with appropriate data management software, enable rapid acquisition and
display of spectral data during voltammetric scans. Early SERS studies of the gold-cyanide
system have been undertaken on colloidal gold [10], or as potentiostatic electrochemical studies
[11]. The technique of simultaneously acquiring SERS and voltammetric data was more
recently applied by Zhang, Gao and Weaver (1993) and is described by these authors as 'real-
time surface-enhanced Raman spectroscopy [12].

Electrochemical SERS activation involves roughening the surface of the electrode by applying
a series of oxidation-reduction cycles (ORCs) in appropriate solutions for gold, silver or copper
electrodes [13]. For a silver electrode, the ORC procedure results in the formation and
dissolution of insoluble silver chloride. In the case of gold and copper, the activation procedure
first dissolves and then redeposits the metal from a quiescent solution onto the surface of the
electrode. The SERS activation procedure therefore has the capacity to alter both the structure
and composition of the gold surface, with obvious ramifications for studies of system purity.
Cathodic electrode cleaning procedures may also contribute to compositional changes by
electrodepositing impurity metal ions from cleaning solutions while attempting to remove
residual chloride resulting from the ORC procedure.

In order to develop the SERS technique as a suitably sensitive in-situ probe of ultra-pure
systems, an initial investigation of the process in AR grade conditions is of benefit. A
spectroelectrochemical investigation using simultaneous cyclic voltammetry and surface-
enhanced Raman spectroscopy (CV-SERS) has been undertaken under such conditions to
establish the effects of SERS activation procedures upon system purity; to observe the effect of
repeated voltammetric cycling of the SERS surface; and to observe effects of the addition of the
impurity ions silver and lead to the AR cyanide solution.

50
 Experimental

Electrochemistry

All reagents used including NaCN, NaOH, NaHCO3, Pb(NO3)2 and AgNO3 were of AR grade.
Solutions of 0.01 mol dm-3 cyanide buffered in NaHCO3 / NaOH to pH 11 were prepared using
high purity water from a Permutit Australia Hi-Pure Water System with typical resistivity of
18 MΩ cm-1. The electrochemical cell and all other glassware were cleaned using 5 mass %
nitric acid (BDH Aristar). Experiments were performed using a custom-designed five-necked
borosilicate electrochemical cell (effective solution volume 75 mL) with an optically flat
transparent window. A conventional three electrode system was used, consisting of an 0.5 mm
diameter platinum wire auxiliary electrode; a silver/silver chloride reference electrode (Cypress
systems EE008, 3.0 mol dm-3 KCl / sat. AgCl electrolyte); and fine (Johnson Matthey 99.5%)
and high-purity (Aldrich 99.999%) gold working electrode of area 1 cm [2]. A vycor-fritted
teflon double junction was used to minimise silver contamination from the reference electrode
during high-purity gold experiments. The gold working electrodes were abraded to expose a
fresh surface using 15 µm grit size P1200 SiC paper, and rinsed with ultrapure water.
Electrodes were sonicated in ultrapure water and placed into a furnace at 450 °C for 30 min to
oxidise any organic contamination. Prior to commencement of voltammetric scans, SERS
electrodes were subjected to oxidation/reduction cycling in 1.0 mol dm-3 KCl solution adjusted
to pH 1 using HCl. Potential control of the cell was established by using an ADInstruments
potentiostat controlled by a Maclab/4e analog-digital converter interfaced to a PC running
ADInstruments EChem software V 1.5.2. The ambient room temperature was 22 °C, resulting
in a silver/silver chloride reference potential of 0.210 V vs SHE [14]. Potentials are reported
relative to this Ag/AgCl reference unless otherwise specified. Scan upper and lower potential
limits were –1.4 and 1.4 V, with a scan rate of 10 mVs-1. Prior to experiments, the cell was
purged by bubbling high purity nitrogen (Linde, 4.0) for 20 min to remove oxygen from the
system. Positive nitrogen pressure was maintained over the cell during the measurement phase
by withdrawing the nitrogen bubbler from solution and flowing gas above the solution surface.

Sers Activation

The SERS electrode was activated by applying an oxidation/reduction cycle (ORC) procedure
in an air saturated 1.0 mol dm-3 KCl solution acidified with HCl to pH 1. The potential regime
consisted of cathodic cleaning for 30 s at –0.7 V, followed by three cycles of potential
switching between –0.5 and 1.0 V, holding at each potential for 30s. At oxidising potentials
gold dissolution was observed, with a yellow colour attributed to AuCl4− visible in the solution
close to the electrode surface. Gold metal was electrodeposited by reduction of the
tetrachloroaurate on the electrode during the cathodic polarisation step, causing a red-brown
coloration of the gold surface. The initial –0.7 V polarisation subjects the electrode to a
cathodic cleaning prior to the ORC process. This potential is within the region of onset of
hydrogen evolution in acidic solution, as evidenced by the formation of bubbles on the surface
of the gold electrode. After resting at –0.5 V for 30s after completion of three cycles of
potential switching, a final -0.7 V polarisation was applied to displace adsorbed chloride from
the surface, and the electrode was withdrawn from solution while held at this potential. Prior to
use in cyanide solutions, the electrode was rinsed with DDI water after removal from the ORC
solution. It was then polarised at –1.0 V for 60 s in a pH 11 buffer solution in equilibrium with
air to remove residual chloride from the SERS surface.

51
 Raman Spectroscopy

SERS spectra were acquired on a Renishaw system 100 Raman spectrometer, using 632.8 nm
excitation from a HeNe laser. The laser spot size was ~ 50 µm, with 6 mW power at the
sample. The Raman scattered light was detected by a peltier-cooled CCD detector with spectral
resolution of 2 cm-1. The laser and scattered radiation were focused through an ultra long
working distance x20 Olympus LMP Plan Fl lens with a numeric aperture of 0.4. The
spectrometer was calibrated against the characteristic lines of neon, with daily offset calibration
referenced to the 520 cm-1 lattice vibration of silicon. SERS spectra were accumulated in static
mode, with scans centered at 670 cm-1 for low frequency modes and 2100 cm-1 for the high
frequency CN stretching region. Spectra were collected for 2 s during potentiodynamic scans,
with a spectrometer rest time of 3 s between scans. The 150 individual Raman spectral scans
acquired over the potential ramp, with the initial scan commenced while the electrode was held
at the lower potential limit. Each scan was acquired over a potential interval of 37.6 mV.
Repeated voltammetric cycling was found to alter both the electrochemical response and SERS
intensity. Accordingly, the first voltammetric run was collected and taken to be representative
of the system. This procedure therefore required a new SERS electrode surface be prepared for
each CV-SERS investigation.
Results and Discussion

Voltammetry of Fine and Pure Gold Electrodes

An investigation was undertaken into the electrochemical characteristics of fine (99.5%) and
pure (5N) gold electrodes prior to SERS activation. In order to minimise contamination during
electrode preparation, the voltammetry of the pure gold electrode was acquired as a first run,
subjected only to furnace cleaning of 1 hr at 450 °C after being shaped from nuggets ‘as
received’. The fine gold electrode was abraded with SiC and cleaned in an ultrasonic bath prior
to a similar furnace treatment. Figure 1 shows a cyclic voltammogram (CV) of a pure gold
electrode without SERS activation acquired in 0.01 mol dm-3 NaCN at pH 11 with scan rate of

Figure 1: Cyclic voltammogram of fine gold electrode in 0.01 mol dm-3

-1
NaCN at pH 11, scan rate 10 mVs ; - furnace treated only - SERS activated.

52
10 mVs -1. The accompanying dashed voltammogram shows the pure gold electrode after
SERS activation and cathodic cleaning in buffer solution. The voltammogram of the
unprepared surface shows little current below –0.6 V. A prominent oxidation peak is evident at
–0.15 V in both forward and reverse scans, indicating that the unprepared electrode undergoes
oxidation at a higher potential than the SERS activated electrode. The voltammograms
presented in Figures 1 and 2 exhibit electrochemical behaviour similar to that reported for
smooth gold electrodes under similar solution conditions [1, 3, 15, 16].

Figure 2: Cyclic voltammogram of fine gold electrode in 0.01 mol dm-3NaCN at

-1
pH 11,scan rate 10 mVs ; - furnace treated only - SERS activated.

Figure 2 shows the effect of SERS preparation on a fine gold electrode. The voltammetry
exhibits peaks at –0.5 V (positive-going) and -0.33 V (negative-going) that suggest the presence
of some lead impurity in the unprepared fine gold sample. The voltammetry of the fine gold
electrode following the SERS procedure is seen to be almost identical to that of the pure gold
sample presented in Figure 1. This would suggest that the SERS activation process normalizes
the purity of the gold surface, removing contamination from the fine gold electrode while
introducing some contaminant species to the surface of the 5N pure gold electrode.

Voltammetry of Fine Gold Sers Electrodes

The CV obtained using a gold electrode in 0.01 mol dm-3 NaCN in pH 11 buffer following
ORC preparation is presented as Figure 3. The ORC procedure results in a plated rough gold
electrode surface. Following the buffer cleaning process, the electrode was inserted into the
cell whilst under potential control of –1.4 V. The electrode was held at this potential for 30 s
prior to commencement of the scan to maintain a potential well below that for the oxidation of
gold in cyanide. Whilst this may contaminate the gold surface by plating trace metal ions from
the solution, it was undertaken in order to maintain a cyanide and oxide free surface prior to
commencement of the scan. The three voltammograms presented in this Figure exhibit
electrochemical behaviour similar to that reported for smooth gold electrodes under similar
solution conditions [1, 3, 15, 16]. It can be seen that addition of 5 ppm lead to the electrolyte
contained in the SERS cell results in an enhanced anodic current in the region above 0.5 V on
the positive-going sweep and the rapid oxide reduction which occurs with a peak at 0.2 V,

53
 Figure 3: Cyclic voltammetry of fine gold SERS electrode in 0.01 mol dm-3 NaCN/pH
11 buffer, 10 mVs-1, after addition of 5ppm Pb, or after addition of 3ppm Ag.

followed by a reduced peak for the facile oxidation of gold in cyanide at 0.16 V. Peaks
characteristic of the oxidation and reduction of lead metal were also observed in the range from
–0.9 to –0.3 V. The smaller facile gold oxidation peak on the negative-going scan observed in
this system at 0.16 V is probably related to the blocking presence of PbO on the gold electrode
surface. PbO will reduce to the metal at negative potentials and expose the gold to cyanidation.
This is apparent in the anodic current peak located at –0.25 V. The resultant gold cyanide
reduces at the same potential observed in Figure 1 CV’s for no addition and for the addition of
3 ppm Ag. When 3ppm silver was present in the buffered cyanide electrolyte the characteristics
of the CV were not altered greatly. However, an increase in the anodic current could be
observed above –0.4 V, and the anodic to cathodic current swing observed on the negative
going potential sweep was of greater magnitude.

CV-Sers of a Fine Gold Electrode

Figure 4 displays 3D terrain renderings of the spectroscopic data acquired during the cyclic
voltammogram for the fine gold ORC electrode in buffered cyanide. The voltammogram is
placed in the centre of this Figure to allow direct comparison with the SERS data. The axes of
the terrain plots are potential, Raman shift and Raman intensity for x, y & z directions
respectively. The vibrational region shown in the plot is the high frequency region centred at
2100 cm-1, in which the vibrational modes of the internal cyanide stretch, νCN, are expected.
Arrows show the direction of the voltammetric scans and the equivalent points on the 3D terrain
plots.

54
 rel. intensity
0
500
1000
2500

1.0

0.8
Current density /m A cm -2

0.6

0.4

0.2

0.0

-0.2

-0.4
-1.4 -1.0 -0.6 -0.2 0.2 0.6 1.0 1.4

Potential /V vs Ag/AgCl

Figure 4: 3D SERS data plotted above and below CV for 0.01 mol dm-3 NaCN
solution in pH 11 buffer. Ramp 10 mVs-1, start –1.4 V, upper 1.4 V.

The upper terrain plot in Figure 4 shows the SERS spectra acquired during the positive going
potential sweep of the voltammogram, while the lower plot runs simultaneously with the
negative going potential sweep. SERS data from the positive going potential sweep shows the
presence of a single cyanide stretching band maintained until the oxidation peak at 0.6 V. After
this oxidation peak the band disappears, replaced by two bands of low intensity shifted to
higher and lower frequencies. The lower frequency band continues to the upper potential limit,
while the high frequency band disappears before the potential where the onset of oxygen
evolution occurs. During the negative-going potential sweep, no cyanide bands are observed
until the reduction and facile oxidation peaks at 0.2 and 0.16 V, respectively.
55
Figure 5: (a) high and (b) low frequency SERS modes accompanying cyclic voltammogram of
gold in 0.01 mol dm-3 NaCN at pH 11 at 10 mVs-1 Solid circles represent free or
surface bonded cyanide compounds, unfilled circles represent cyanate and squares
represent gold-oxide vibrational modes. The variation in Raman background
intensity is included as a continuous light-weight line in both (a) and (b).

Following this electrochemical feature, the strong SERS band shows that cyanide returns at the
surface of the electrode, indicating the reduction and removal of a non-cyanide passivating
layer immediately followed by an oxidative cyanidation reaction. The cyanide stretching band
is then retained to the lower potential limit. Scans presented in this form, although useful for
observing Raman peak intensity and the variation in intensity of Raman background scattering,
do not provide adequate detail of shifts in band positions.

Figure 5 presents vibrational band position data extracted from SERS spectra, plotted as Raman
shift vs. time-based potential, in order to better observe changes in Raman frequency during
voltammetric ramps. Spectral data from low wavelength regions is included with data from the
higher frequency cyanide stretching region, increasing the vibrational information available
56
with which to interpret the nature of surface or solution species accompanying electrochemical
events. Extracted spectral data from high and low wavenumber regions are presented above
with a time-based representation of the typical voltammogram. The high frequency region (a)
displays extracted spectral data in the region of the cyanide stretch, νCN, centred at 2100 cm-1,
while the low frequency region (b) shows data centred at 670 cm-1. It is in the latter region that
the gold-oxygen stretch, νAuO, gold-carbon stretch, νAuC, and gold-carbon-nitrogen deformation,
δAuCN, are observed.

The vibrational frequency of the cyanide ion in simple solids such as NaCN and KCN is known
to be 2070 – 2080 cm-1, and 2080 cm-1 in solution 10. Figure 3(a) shows a cyanide νCN mode
at 2075 cm-1 at the starting potential and this can be assigned to free cyanide. Linear Stark-
tuning of the free cyanide, νCN from 2075 cm-1 at the lower potential limit to 2105 cm-1 at the
onset of cyanidation is observed at 55 cm-1V-1 during the positive-going sweep. The
assignment of νCN within the range of potentials from –1.4 V to –0.84 V to the free ion is
confirmed by the absence of low frequency metal-ligand modes in this potential region (3(c)).
The appearance of the low frequency modes νAuC, 350 cm-1 and δAuCN, 290 cm-1
concurrent with the electrochemical onset of cyanidation provides evidence of chemisorption of
cyanide upon the gold surface. With the onset of the metal-ligand modes, dνCN/dE ceases to
be linear and curves to form a plateau by 0.5 V. At this potential, the νCN of the surface
bonded cyanide reaches a maximum value of ~ 2130 cm-1, with the lower frequency modes
reaching values of 395 cm-1 for νAuC and 295 cm-1 for δAuCN. The final passivated
oxidation peak on the positive-going sweep prior to the oxygen evolution reaction in Figure
3(b) is also seen to occur at 0.5 V, and is concurrent with the disappearance of both metal-
ligand vibrational modes.

Cyanate is the expected electrochemical oxidation product above an applied potential of about
0.65 V for this system. This is confirmed by the appearance of the band at 2165 cm-1 above
this potential. A small band at 2113 cm-1 is also observed in this potential region which we
assign to the adsorption of cyanide. Figure 3 indicates that this event is associated with the
disappearance of both metal-ligand vibrational modes. This could arise, however, from a much
lower cyanide coverage. The intensity of the νAuC and δAuCN bands is close to an order of
magnitude less than that of the associated νCN vibration and hence may not be discernible from
the background in this potential region on a CV-Raman. The energy of the 2113 cm-1 band is
similar to that described by Baltruschat and Heitbaum as being due to cyanide adsorbed upon a
gold surface at –0.8 V vs. SCE.10 The formation of a well characterised band due to gold
oxide12 occurs at ~ 1.0 V and is maintained beyond the upper potential limit of the positive
going potential scan.

During the negative going potential scan, no evidence of νCN is observed until the passivating
oxide layer is reduced at ~ 0.2 V. At this potential, νCN bands return at 2170 and 2130 cm-1,
with the higher band, assigned to cyanate, disappearing by –0.2 V. The 2130 cm-1 band
assigned as being due to a surface cyanide species undergoes slow linear Stark-tuning until the
current becomes reducing at –0.6 V. At this potential, the Stark-tuning rate increases until a
steep linear slope is established by –1.2 V. The frequency of the νCN at the lower potential is
2070 cm-1, similar to that of the free cyanide at the start of the positive-going scan. Both low
frequency metal-ligand modes are observed at potentials lower that of adsorption, with the
δAuCN particularly being strongly retained to the lower potential limit.

The derived data presented in Figure 5 is obtained from individual Raman spectra, the intensity
and resolution of which is a function of the vibrational mode and the quantity of material.
Figure 6 presents SERS spectra recorded on the positive going scan of the CV for fine gold in
57
buffered cyanide. These spectra show the relative intensity of the Raman bands and provide an
indication of the relative quantities of the SERS active species. It should be noted that the
SERS spectra are up to seven orders of magnitude more sensitive than normal Raman. The
νAuO observed at 1.4V is derived from a thicker layer than the other spectra. The observed band
is broad, reflecting the structure of the gold oxide layer formed during CV.

1.4 V
Raman intensity / arb. units

0.83 V

0.4 V

- 0.6 V

- 0.8 V

- 1.4 V

Raman shift / cm-1

Figure 6: SERS spectra recorded on the positive-going scan of a 10 mV s-1 cyclic
voltammogram at a gold electrode in 0.1 mol dm-3 NaCN solution when the
potential was at –1.4 V, –0.8 V, –0.6 V, 0.4 V, 0.83 V and 1.4 V in the νCN (left)
and νAuC, νAuO and δAuCN region (right). The intensity scale for the bottom four left-
hand spectra is 6x that for the others.

Sers of a Fine Gold Electrode in the Presence of 5 PPM Lead

The addition of lead ions to the spectroelectrochemical cell (5 ppm) was shown to result in
substantial changes to the fine gold CV, attributable to the reduction and oxidation of lead
species at the fine gold electrode. Selected Raman spectra from the positive going scan of the
CV are presented as Figure 7. The general form of these spectra correspond to those for the
buffered cyanide presented in Figure 4, however there are two major differences. Firstly, the
signal to noise ratio was greatly improved for the νCN whilst the νAuC, νAuO and δAuCN region
appeared to be largely unchanged by the presence of lead in the electrolyte. Secondly, with the
addition of lead, there was only a barely detectable cyanate SERS band detected. It is possible
that both these observations are attributable to the alteration of the electrode surface caused by
the deposition and oxidation of lead (a SERS effect), however in this case we would expect to
see both spectral regions enhanced. It is expected that the solution lead species will plate onto
the fine gold surface when the potential is held at the start value of –1.4V. The CV for the lead
addition presented in Figure 3 exhibits an oxidation peak, attributable to lead being oxidized at
-0.6 V and an increased current density in the oxide passivation region compared to the
buffered cyanide system. Jeffrey and Ritchie3 concluded that lead is located on the gold surface
under conditions similar to those incorporated in this investigation. Accordingly, lead cyanide
58
anion will not be the major oxidation product at this potential. This is supported by the lack of
a significant SERS cyanate band in the Raman spectra above 0.4 V which further indicates that
the gold surface has been modified, reducing the tendency of the system to generate gold
cyanate at the surface, possibly through the presence of lead oxide and subsequent modification
of the oxygen generation process.

1.4
1.4 V
V
Raman intensity / arb. units

1.0 V
1.0

0.4
0.4 V
V

0.6 V
--0.6

--0.8
0.8 V

--1.4 V
1.4 V

2200 2100 2000 900 700 500 300

-1
Raman shift / cm

Figure 7: Raman spectra recorded on the positive-going scan of a 10 mV s-1 cyclic

voltammogram at a gold electrode in 0.1 mol dm-3 NaCN solution, 5 ppm Pb,
when the potential was at –1.4 V, –0.8 V, –0.6 V, 0.4 V, 1.0 V and 1.4 V in
the νCN (left) and νAuC, νAuO and δAuCN region (right).

Sers of a Fine Gold Electrode in the Presence of 3 PPM Silver

In the case of the addition of silver ions to the buffered cyanide system, the intensity of the
SERS spectra (Figure 8) increased significantly, with those spectra measured at high wave
numbers approximately two times more intense than those recorded for the cyanide system
without added silver. In addition, the onset of gold oxide formation is associated with more
intense cyanate and surface cyanide species compared to the system without added silver. The
cyanide band also increased relative to that of the cyanate. These effects, possibly, could be
attributable to a SERS effect generated by the presence of silver sites adjacent to the gold
species, but if this were the case we would expect all bands to be intensified proportionately. It
is probable that the silver is forming dicyanide anions as well as gold. This is supported by the
asymmetric broadening of the band observed at 2110 cm-1 indicating the presence of two SERS
active cyanide complexes, and the reported SERS band position for silver dicyanide.17,18 There
are sufficient silver ions present in solution to generate the formation of silver cyanide as
observed in the Raman spectra. The other oxidation processes observed by Raman
spectroscopy with the silver addition correspond to those of the cyanide system without silver
addition.

59
 1.4 V
Raman intensity / arb. units

0.76 V

- 0.4 V

- 0.6 V

- 0.8 V

- 1.4 V

Raman shift / cm-1

Figure 8: Raman spectra recorded on the positive-going scan of a 10 mV s-1 cyclic
voltammogram at a gold electrode in 0.1 mol dm-3 NaCN solution, 3 ppm Ag,
when the potential was at –1.4 V, –0.8 V, –0.6 V, 0.4 V, 0.76 V and 1.4 V in
the νCN (left) and νAuC, νAuO and δAuCN region (right). The intensity scale for
the bottom four left-hand spectra is ~ 10x that for the others.

Extracted Data from CV-Sers of a Fine Gold

Electrode in the Presence of Silver or Lead

Figure 9 presents the vibrational band position data extracted from SERS spectra, plotted as
Raman shift vs. time-based potential together with the CV’s for silver and lead additions. The
CV for the system containing 3 ppm silver is similar to that for the system with no addition,
except for an increased cathodic current at potentials below –0.8 V due to silver ion reduction,
and an increase in the anodic current in the gold cyanidation region. The SERS spectral data is
also similar to the result obtained for the system with no additions presented and described in
Figure 5. The CV for the lead addition system is described following Figure 3; the data shows
enhanced anodic currents in the gold cyanidation and oxidation regions, and initial inhibition of
the facile cyanidation of gold on the negative-going sweep following gold oxide reduction. The
effect of addition of lead to the Raman bands observed is most apparent in the potential region
where gold oxide leads to passivation of the gold surface (above ~ 0.5 V vs Ag/AgCl). The
SERS νCN band from AuCN disappears at ~ 0.8 V, but reappears again at ~ 0.9 V. Also, in the
higher potential region, there are barely discernible νAu-C and δAuCN bands. This indicates that
there is unbonded CN- present near the gold surface, with a band located at a frequency similar
to that observed for cyanide bonded to gold prior to the commencement of oxide growth. The
intensity of the νCN becomes negligible again just before the upper limit of the scan and is not
discernible again until gold oxide is reduced on the return scan. On the other hand, bands at
frequencies we have assigned to νAu-C and δAuCN, remain discernible throughout the gold oxide
potential region, even though their intensity is very low. Further work is required to identify
the cause of this behavior.

60
Figure 9: High and low frequency SERS modes accompanying cyclic voltammogram of
gold in 0.01 mol dm-3 NaCN at pH 11 at 10 mVs-1 Solid circles represent
spectra obtained in the presence of lead, unfilled circles represent spectra
obtained in the presence of silver. CV’s for lead and silver additions are
presented for reference.

The onset of the oxygen anodic peak in the CV is accompanied by the reappearance of νAu-C
and δAuCN bands at lower band energies, but not the νCN band. Therefore, though we do observe
the gold – carbon stretch and the gold – carbon – nitrogen bending modes, we do not observe
the carbon – nitrogen triple bond stretching vibration which would be present if the product was
gold cyanide or cyanate. This proposed change in the bonding structure is consistent with the
lower band frequencies for the low frequency region observed in the case of lead ion addition to
the system. The νAu-C and δAuCN bands are lost when the negative-going scan reaches 0.4 V,
and do not reappear until the gold oxide reduction occurs at 0.2 V, when their band energy is
characteristic of gold cyanide on the gold surface.

61
 Conclusions

Cyclic voltammetry with roughened gold electrodes in pH 11 buffered 0.01 mol dm-3 NaCN
solutions have been found to be in agreement with studies by other authors using smooth gold
surfaces in dilute cyanide systems. Extracted data plots of the Raman vibrational modes of the
cyanide system in the absence of added impurity species, or in the presence of added silver
(3 ppm) or lead (5 ppm) show that a solution cyanide species is specifically adsorbed at the
interface prior to the onset of gold cyanidation. Raman bands indicative of cyanide oxidation to
cyanate are observed at high potentials, however, these are more intense when silver is present
than in the lead case. The Raman spectra obtained in the region of gold oxide formation when
lead is present reveal the formation of gold-carbon-nitrogen bonding which does not contain
carbon-nitrogen triple bonds. Raman spectroscopy has shown that the presence of 3 ppm of
silver in the buffered cyanide electrolyte did not change the SERS active species present during
the CV SERS experiments.

Acknowledgements

The authors thank Griffith University for the award of a research grant.

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