Hydrometallurgy 127–128 (2012) 43–53

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Kinetic studies of gold(III) chloride complex reduction and solid phase precipitation
in acidic aqueous system using dimethylamine borane as reducing agent
Marek Wojnicki ⁎, Ewa Rudnik, Magdalena Luty-Błocho, Krzysztof Pacławski, Krzysztof Fitzner
AGH University of Science and Technology, Faculty of Non-Ferrous Metals, Department of Physical Chemistry and Metallurgy of Non-Ferrous Metals, al. Mickiewicza 30,
30‐059 Cracow, Poland

a r t i c l e i n f o a b s t r a c t

Article history: Kinetics of gold(III) chloride complex ions reduction with dimethylamine borane and precipitation of gold
Received 8 December 2011 nanoparticles was investigated. The influence of concentrations of reductant, gold(III) chloride complex
Received in revised form 28 April 2012 ions, neutral salt and chloride ions as well as temperature on the process was reported. Experimental results
Accepted 25 June 2012
were used to determine parameters in the Arrhenius equation. A set of reactions occurring in the system was
Available online 6 July 2012
proposed. Rate equations were presented and verified. It was proposed that state of the catalytic surface of
Keywords:
gold particles play a crucial role in the mechanism of the reaction and competition between AuCl4− adsorption
Gold recovery and AuCl4− reduction on the metal particles exists in the system. Microscopic observations as well as analysis
Kinetics of the particles were also performed.
Reduction © 2012 Elsevier B.V. All rights reserved.
Metal precipitation
DMAB

1. Introduction There is a lack of information on the kinetics of reaction between

KGHM Polska Miedź S.A. is one of the biggest producers of copper,
silver and gold in Europe. In 2008, 924 kg of gold and more than 1200
tons of silver were produced in the plant as side products (KGHM,
2011). Noble metals (Au, Pt, Pd) are recovered in several steps from a
slime after silver electrorefining. Initially, the slime is leached in
hydrochloric acid to remove copper and bismuth contaminations. Pre-
cious metals remained in the solid phase are then dissolved in 10%
HCl in the presence of gaseous chlorine. In next stages, gold chloride
complexes are reduced to metal using disodium disulphite (pH 0.2,
323 K), whereas palladium, platinum and remaining gold ions are pre-
cipitated from the solution using sodium formate (pH 2.5, 353 K). Puri-
fied solution is finally transferred to the waste-water treatment plant.
Technology used currently in the Polish plant seems to be costly, since
losses of precious metals (0.005 g/L in the waste solution), consumption
of energy and reductants are quite significant. This inspired us to devel-
op an alternative method for selective recovery of noble metals present
in an acid chloride solution. From a number of various compounds,
dimethylamine borane (DMAB) can be proposed as an alternative for
HCOONa reductant. It shows good reactivity towards noble metals at
ambient temperature. This reductant has been widely used in electro-
less deposition of gold (Sadik et al., 2005; Sargent and Sadik, 2001;
Sargent et al., 2001) or palladium (Lelental, 1973), although application
for synthesis of platinum or gold nanoparticles was also reported (Hüttl
et al., 2009; Wojnicki and Fitzner, 2011).
⁎ Corresponding author. Tel./fax: +48 126174126.
E-mail address: marekw@agh.edu.pl (M. Wojnicki).
noble metal ions and DMAB. Our previous study (Wojnicki et al.,
2011) was focused on the kinetics of reduction of palladium(II) chlo-
ride complex using DMAB. The aim of the present paper was to deter-
mine the rate equation as well as mechanism of the reaction between
gold(III) chloride complex and DMAB. The effect of gold(III) ions, Cl −
ions and DMAB concentrations, ionic strength of the solution and
temperature on the reaction rate was studied. The knowledge on
the kinetics can help to select the best conditions for the selective re-
duction of palladium and gold complexes in acidic chloride solutions.
2. Experimental
Solution of gold(III) chloride complex was prepared from metallic
gold (99.99%, provided by Mennica Polska S.A.). Metal was dissolved
in aqua regia, and then mixture was evaporated several times to remove
nitric acid and excess of HCl to obtain pure solid tetrachloroauric acid.
Next, the acid was dissolved in deionized water. Required concentra-
tions of gold(III) chloride complexes (2.5 × 10−5 to 2.5 × 10 −4 M) in
the investigated solutions were achieved by an appropriate dilution of
the initial solution with 0.1 M HCl (from Chempur, p.a.). Total Cl− con-
centration in the solutions was maintained in the range of 0.05–1.05 M
by addition of NaCl (from POCh, >99.9%). DMAB (from Fluka, >97%)
was dissolved in deionized water. Concentrations of the reductant
were changed in the range of 1.25–25 mM. Neutral salt NaClO4 (from
Koch-Light Laboratories Ltd.) in the concentration range of 0.125–1 M
was used to salt effect studies. pH of solutions was 1.7. Experiments
were carried out at temperatures from the range of 288–318 K.

0304-386X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.06.015
44 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53
Changes of gold(III) chloride complex ions concentration during
reaction with DMAB was measured spectrophotometrically. All ex-
periments were carried out by means of spectrophotometer (Applied
Photophysics SX-20) using stopped flow technique. Directly before
spectrophotometric analysis two solutions (AuCl4− and DMAB) were
mixed in a T-shape micromixer in the 1:1 volume ratio to obtain
proper concentrations of the reactants. Turbidimetric analysis was
applied for monitoring precipitation of metallic particles.
Droplets of gold colloid (sample was taken one minute after syn-
thesis, [AuCl4−]0 = 1.25 × 10 − 4 M, [DMAB]0 = 25 × 10 − 3 M, [Cl −]0 =
0.05 M, T = 298 K) were dripped over a copper grid coated with
amorphous carbon layer (20–30 nm) and then dispersant was evap-
orated at room temperature. Particles of metallic gold were analyzed
by means of STEM microscope (Hitachi SU-70, Thermo Science) using
EDS (Energy Dispersive X-ray Spectroscopy) and EBSD (Electron Back
Scatter Diffraction) methods. To determine particles' size and size distri-
bution an image analysis was performed using ImageJ1.45s software.
3. Results
3.1. Reduction of AuCl4−
3.1.1. Distribution of gold(III) species
The effect of pH on the distribution of gold(III) complex ions at
constant chloride ions concentration (0.05 M) was calculated. Calcu-
lations were done using experimental data reported by Hönes et al.
[Hönes et al., 1992). Fig. 1 shows that in the studied system (pH
1.7) only one form of gold(III) can exist in the solution. Hence, it
was assumed that solely AuCl4− ions can participate in the reaction
with DMAB.
3.1.2. Kinetics of AuCl4− reduction
Fig. 2 shows spectra of pure AuCl4− solution for three different ini-
tial concentrations. The presence of AuCl4− ions is indicated by two
strong (226 nm and 314 nm) and one weak (approx. 400 nm)
peaks in the UV–VIS range. For further investigations the wavelength
of 314 nm corresponding to ligand-metal charge transfer was chosen
for monitoring the changes of Au(III) ions concentration during reac-
tion with DMAB. It was mainly imposed by the limitations of the ap-
paratus (Applied Photophysics SX-20) used in this study, since its
maximum absorbance at the wavelength of 226 nm (at the path
length of 1 cm) is solely 2.2 at relatively high molar absorption
Fig. 1. pH-dependent distribution of gold(III) species ([Au(III)]0 = 5 × 10−4 M, [Cl−]0 =
0.05 M, T= 298 K).
Fig. 2. UV–VIS spectra of AuCl4− solution of various concentrations.
coefficient (35,750 M −1.cm −1), hence, only experiments with solu-
tions of very low AuCl4− concentrations could be performed.
DMAB does not exhibit any peaks for the wavelengths in the range
from 200 nm up to 900 nm.
Fig. 3 shows changes of the solution absorbance during reaction of
gold(III) chloride complex with DMAB. Gradual decay of the peaks
characteristic for AuCl4− ions was observed. Simultaneously, new
wide peak at the wavelengths in the range of 500–600 nm appeared
in the spectrum and the color of the solution changed via red to
blue. It shows that colloidal metallic gold particles can form as a prod-
uct. It is known (Basiński, 1957) that nanometric gold particles can
disperse, but also absorb, light of a wavelength dependent on the par-
ticles' size, shape and structure. The change of the colloid color with
time indicates that size of the particles increased from 25–35 nm
(red sol) to 70–80 nm (blue sol). It corresponded to the change of
the wavelength absorbed from approximately 530 nm to approxi-
mately 600 nm. Relatively small shift of the peak maximum towards
higher wavelengths with time (Fig. 3) confirms that mean size of the
precipitated particles does not rise drastically. Moreover, a width of
the peak does not change significantly. It suggests that particles'
size distribution is maintained in the same range. For further moni-
toring of the metal particles precipitation spectrophotometry and tur-
bidimetry (at 600 nm) were used.
It was also observed that the presence of metallic gold in the solu-
tion facilitated hydrogen evolution. It is one of the typical side prod-
ucts of DMAB oxidation.
An exemplary kinetic curve registered during gold(0) precipita-
tion is shown in Fig. 4. Turbidance of a colloidal suspension is depen-
dent on the wavelength of the light transmitted through the sample
λ, path length l as well as mean size d and concentration c of colloidal
particles. This dependence can be approximated by the Wells equa-
tion (Weston and Vishniac, 1969):
k⋅d3 ⋅l⋅c
T¼ ð1Þ
d4 þ a⋅λ4
where: T — turbidance; k, a — constants dependent on the measure-
ment method and a type of colloidal suspension.
For monochromatic light, Eq. (1) can be written as modified
Lambert–Beer law:
0
T ¼ ε ⋅l⋅c ð2Þ
 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53
Fig. 3. Changes of solution spectra during reaction. Experimental conditions: [AuCl4−]0 = 1.25 × 10−4 M, [DMAB]0 = 25 × 10−3 M, [Cl−]0 = 0.05 M, T = 298 K.
where:
3 phase in the solution (dissolution of the particles is rather not possible).
0 k⋅d
ε ¼
4
d þ a⋅λ4
Kinetic curves registered during turbidimetric measurements
have characteristic sigmoidal shape, specific for autocatalytic process,
where product of the reaction is a reaction catalyst (here: gold parti-
cles) (Cao et al., 2006). Three stages of gold precipitation can be dis-
tinguished: initiation of the process (in Fig. 4: from the reaction
start at t = 0 s to t = 0.12 s), growth of the nuclei (from t = 0.12 s to
maximal turbidance at t = 0.2 s), coagulation of the particles (from
the turbidance maximum at t = 0.2 s to the end of the process). At
first stage very fine metallic nuclei are formed. Low rate of the process
is determined by relatively small increase in the amount of crystalli-
zation nuclei during homogenous reaction between AuCl4− and reduc-
tant. Moreover, most of the produced metallic phase is in the atomic
fineness and practically does not participate in the scattering of the
light. When solid phase appears in the solution a rapid increase in the
reaction rate is observed due to catalytic properties of gold particles to-
wards DMAB oxidation. The rate of the particles growth is generally a
linear function of time if sufficient amount of the crystallization nuclei
is present in the system. A slight decrease in the turbidance in the last
Fig. 4. Kinetic curve of gold precipitation. Experimental conditions: T = 298 K,
[DMAB]0 = 12.5 × 10−3 M, [AuCl4− ]0 = 2.5 × 10−4 M, [Cl−]0 = 0.05 M, λ = 600 nm.
45
stage indicates that fine gold particles (red sol) create aggregates
(blue sol) resulting in apparently smaller concentration of the solid
ð3Þ It is proved (Basiński, 1957) that red soles of gold consist of primary
particles, while in the blue ones aggregates of the primary particles
are present, and the change in the colloid color corresponds to the in-
crease in the particles' size during coagulation.
Kinetic curves as a dependence of solution absorbance versus time
were registered at the wavelengths of 314 nm and 600 nm for AuCl4−
and Au°, respectively. All measurements were repeated five times.
Fig. 5 shows exemplary curves registered for AuCl4− and Au°.
It was assumed that increase in the absorbance (at 600 nm) ob-
served during the reaction was mainly due to the increased concen-
tration of gold particles in the solution with narrow distribution of
the particles' size (red sol) (Liu et al., 2007). Sigmoidal shapes of
both curves confirm autocatalytic mechanism of the reaction. It is in-
teresting that intersection of the curves does not occur at a half wave,
but below it. Apparently, it may show that AuCl4− ions disappear
faster than gold particles are formed (the rate of the particles' forma-
tion may be the same or lower than the rate of AuCl4− reduction). In
fact, absorbance registered at 600 nm originating from the surface
plasmon resonance of gold nanoparticles (Jain et al., 2006) does not
have to involve any quantitative information on the reaction course
Fig. 5. Kinetic curves representing gold(III) chloride complex consumption and gold(0)
precipitation. Experimental conditions: [AuCl4−]0 =2.5×10−5 M, [DMAB]0 =12.5×10−3 M,
[Cl−]0 =0.05 M, T=318 K.
46 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53

(Cao et al., 2006) and its interpretation may lead to incorrect

conclusions.
Data presented in Fig. 5 show that change in the concentration of
gold(III) ions during the initiation stage is negligible due to formation
of very fine metallic nuclei in homogeneous reaction between AuCl4−
and DMAB, but it varies rapidly when solid phase appears in the solu-
tion. Hence, it was accepted that reaction between AuCl4− and DMAB
occurring on the previously formed metallic nuclei can be described
by the following summary equations for homogenous and heteroge-
neous path, respectively:

k1
HAuCl4 þ ðCH 3 Þ2 NHBH3 þ 3H2 O → Au↓ þ H 3 BO3 ð4Þ
3
þ4HCl þ ðCH3 Þ2 NH þ H2 ↑
2

k2
HAuCl4 þ ðCH 3 Þ2 NHBH3 þ 3H2 O þ Au → 2Au↓ þ H 3 BO3 ð5Þ
3
þ4HCl þ ðCH 3 Þ2 NH þ H2 ↑
2 Fig. 6. Influence of initial concentration DMAB on the rate constant. Experimental
conditions: [Cl−]0 = 0.05 M, T = 288 K.
Reaction (5) is both consecutive and parallel to the process (4).
To determine consumption of AuCl4− the Finke–Watzky model
based on two reactions relating to the autocatalytic process was
It seems that heterogeneous reaction can occur in the absence of
adopted from the literature (Finney and Finke, 2008):
DMAB, since k2,obs can be determined from the extrapolation of the
k1 straight lines to the ordinate axis. It is in a conflict with a definition
A→B ð6Þ of k2,obs specified earlier. However, such discrepancy may result
from the adsorption of AuCl4− ions on gold particles precipitated in
k2
A þ B → 2B ð7Þ the homogenous stage (Cao et al., 2006). This leads to the decrease
of gold(III) ions amount without DMAB consumption. Moreover, the
Change of A concentration with time is described by a general decrement of AuCl4− ions from the solution should be visible more
equation: clearly at higher gold(III) concentration due to establishment of the
adsorption equilibrium. It reveals as a decrease in the observed rate
½A0 þ kk1 constant k2,obs, which is in the accordance with the data presented
½A  ¼ 2
ð8Þ in Fig. 6.
1 þ k k½A1  ⋅eðk1 þk2 ½A0 Þ⋅t
2 0

Value denoted with subscript “0” corresponds to the initial con- 3.1.4. Influence of gold(III) chloride complex initial concentration
centration of A in the solution. The influence of the initial concentration of gold(III) chloride com-
Eq. (8) was rearranged for the considered case: plex ions on the reaction rate was investigated. Tests were performed
at two temperatures and constant DMAB concentration. It was found
½AuCl4 − 0 þ k1;obs
k that k2,obs decreases with increased AuCl4− concentration (Fig. 7). It
−
½AuCl4  ¼ n
2;obs
 o ð9Þ shows that Au(III) ions are utilized in a few separate processes and de-
k1;obs k
1þk − ⋅ exp k1;obs þ ½AuCl4 − 0 k2;obs t termined experimentally rate constant k2,obs may combine in fact rate
2;obs ½AuCl4 0 2;obs

constants of some parallel or subsequent heterogeneous processes.

It was accepted that concentration of DMAB is at least one order
higher than that of AuCl4−, hence, k1,obs = k1 ⋅ ε ⋅ [DMAB]0and k2,obs =
k2 ⋅ ε ⋅ [DMAB]0where k1 and k2 are actual rate constants of Reactions
(4) and (5), while ε is molar absorption coefficient at 314 nm
(5400 M −1.cm −1). Observed rate constants k1,obs and k2,obs can be
determined from the fitting of the Eq. (9) to the experimental kinetic
curves. For example, for [AuCl4−]0 = 2.5 × 10 −5 M, k1,obs/k2,obs ratio
equals to 10 −10. This value indicates that Reaction (5) dominates in
the system.
To confirm validity of the proposed model series of experiments
were performed and the results are gathered in the next chapters.

3.1.3. Influence of DMAB initial concentration

The influence of initial concentration of DMAB on the observed re-
action rate constant k2,obs was studied. The investigations showed lin-
ear dependences of k2,obs vs. DMAB concentration (Fig. 6), but the
plots do not intercept the origin of the coordinate system. Moreover,
k2,obs is dependent on the AuCl4− initial concentration and at constant
DMAB concentration k2,obs reaches higher values for lower AuCl4−
amounts in the solution. Both observations suggest that studied pro-
cess is complex and more than one reaction paths of AuCl4− reduction Fig. 7. Influence of initial concentration of gold(III) chloride complex ions on k2,obs.
can occur in the system. Experimental conditions: [Cl−]0 = 0.05 M, [DMAB]0 = 0.05 M.
 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53 47

Characteristic shape of the curves confirms that AuCl4− ions can adsorb Table 1
on the gold particles (Biggs et al., 1994; Cao et al., 2006) and therefore Influence of temperature on k2,obs. Experimental conditions: [DMAB]0 = 12.5 × 10−3 M,
[Cl−]0 = 0.05 M.
inhibit adsorption of DMAB molecules due to occupation of the adsorp-
tion sites by complex gold ions. This effect is more emphasized for T, K [AuCl4−]0 =2.5×10−4 M [AuCl4−]0 =1.25×10−4 M [AuCl4−]0 =5×10−5 M
higher concentrations of gold chloride complex and it may be assumed k2,obs, s−1 ln(k2,obs) k2,obs, s−1 ln(k2,obs) k2,obs, s−1 ln(k2,obs)
that monolayer adsorption of ions exists in the studied system.
288 47.28 3.86 82.90 4.42 179.78 5.19
Adsorbed ions behave as a barrier layer for exchange of electrons be- 298 81.08 4.39 141.18 4.95 318.87 5.76
tween the reductant and precursor via metallic gold catalytic surface. 308 150.30 5.01 246.03 5.50 542.69 6.30
An attempt of the reaction order determination was made. As it 318 244.38 5.50 373.66 5.92 808.02 6.69
was mentioned earlier, heterogeneous reaction dominates in the sys-
tem. Therefore, the reaction rate was calculated upon the changes of
AuCl4− ions concentration with time (linear dependence) registered
in the second stage of the process (Fig. 8a). General equation describ- To determine activation energy of the process Ea, the Arrhenius
ing the reaction rate v for this step is: equation was used:

k2;obs ¼ A⋅eð R⋅T Þ

−Ea
d½AuCl−
4  α − β − β ð12Þ
v¼− ¼ k2 ⋅½DMAB0 ½AuCl4 0 ¼ k2;obs ½AuCl4 0 ð10Þ
dt
where A — pre-exponential factor, T — temperature, R — gas constant.
where α and β are reaction orders with respect to DMAB and AuCl4− Fig. 9 shows linear dependences of ln k2,obs versus 1/T. Ea and A were
concentrations, respectively. Actual reaction order with respect to determined from the slopes and intercepts of the straight lines with
AuCl4− concentration was then determined graphically using logarith- the axis of ordinates, respectively. The obtained values are summa-
mic form of Eq. (10): rized in Table 2.
It was found that activation energy increases only slightly with the in-
−
logv ¼ logk2;obs þ β log½AuCl4 0 ð11Þ crease in AuCl4− concentration, but its average value is 39.8±2.1 kJ/mol.

3.1.6. Influence of chloride ions concentration

this represents a linear dependence (Fig. 8b) with the slope of β.
It was found that in the AuCl4−–DMAB system reaction order β is
1.32 at 288 K and 1.24 at 298 K. Eq. (10) does not account adsorption
phenomenon occurring in the system and fractional value of the reac-
tion order confirms that mechanism of the process is complicated.
Small difference between values determined at two temperatures is
due to experimental error or it suggests that component reactions
are not dependent on the temperature in the same manner.
3.1.5. Influence of temperature
Experiments were carried out at temperatures in the range from
288 K to 318 K. Values of k2,obs were determined by fitting of
Eq. (9) to kinetic curves registered for various initial AuCl4− concen-
trations at constant concentration of the reductant. Obtained values
are given in Table 1. It was found that increase in the temperature fa-
cilitates reduction of gold ions, but an increase in the AuCl4− concen-
tration decreases k2,obs.
To determine the influence of chloride ions on the reaction kinet-
ics, different initial concentrations of sodium chloride was added. The
experimental results are given in Fig. 10.
It was observed that at constant temperature, k2,obs decreased with
increased Cl− concentration and excess of chloride ions in the solution
can inhibit the reduction of AuCl4− ions with DMAB. For comparison, the
effect of neutral ClO4− ions on k2,obs was presented in Fig. 10, but in this
case an opposite effect was observed. It shows that Cl− ions play an es-
sential role in the reaction course, while ClO4− ions can only affect the
ions participating in the process by shielding according to the salt effect
theory, since ClO4− is an anion weakly adsorbing on Au surface (Garland
et al., 2002).
For better understanding the process, the influence of chloride
ions on the reaction rate at different temperatures was investigated.
Obtained results and fitted linear dependences are shown in Fig. 11.
It was found that the increase in the initial concentration of chlo-
ride ions increases activation energy of the process from 42.22 kJ/mol

Fig. 8. Determination of the reaction order in respect to AuCl4− concentration. Experimental conditions: [DMAB]0 = 12.5 × 10-3 M, [Cl−]0 = 0.05 M.
48 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53

Fig. 9. The Arrhenius dependence for the reaction between AuCl4− and DMAB. Experi- Fig. 10. Influence of the initial concentration of chloride and perchlorate ions on k2,obs. Ex-
mental conditions: [DMAB]0 = 12.5 × 10−3 M, [Cl−]0 = 0.05 M. perimental conditions: [AuCl4−]0 =2.5×10−4 M, [DMAB]0 =12.5×10−3 M, T=298 K.

for [Cl −]0 = 0.05 M to 55.9 kJ/mol for [Cl −]0 = 1.05 M. The change of ions on gold electrode is strong, since they form polar chemisorption
the activation energy suggests that chloride ions can participate di- bonds with the metal surface. Similar effect was reported by
rectly in the reaction between AuCl4− and DMAB. Alexandridis (2010) and Lee et al. (2009) who found that adsorption
To clarify the effect of Cl − ions on the reaction rate two possibili- of chloride ions can affect a shape and size of precipitated gold
ties were considered. The reaction between AuCl4− and DMAB can be nanoparticles. It is worth also to note that Cl − anions have much
explained according to electrochemical theory commonly accepted lower affinity for gold surface in comparison to AuCl4− adsorption
for electroless plating. It assumes that two partial reactions (AuCl4− (Biggs et al., 1994) and inhibition of the process was observed for
reduction and DMAB oxidation) are not independent of each other higher chloride ions concentrations than for gold chloride ions.
and run simultaneously at the same potential. A necessary condition
for Reactions (4) and (5) to occur is that the equilibrium potential 3.1.7. Salt effect
for the reducing agent oxidation is more cathodic than the It is known that addition of some amount of neutral salts to the in-
corresponding potential for the metal deposition: vestigated system may increase, decrease or have no influence on the
reaction rate. This effect has been called “salt effect”. The effect of the
− −
AuCl4 þ 3e→Au þ 4Cl ð13Þ salt addition is dependent on the charge of reacting species. Using fol-
lowing equation:
Equilibrium potential for Au/AuCl4− electrode defined by Nernst
! pffiffi
equation k2;obs I
log ¼ 2⋅a⋅zA ⋅zB ⋅ pffiffi ð15Þ
k2;obs;0 1þ I
o RT ½AuCl 4
Eo;AuCl =Au ¼ EAuCl =Au þ ln ð14Þ
4 4 3F ½Cl 4
where k2,obs,0 — reaction rate constant in the absence of neutral salt;
indicates that increase in the Cl − concentration is accompanied by a k2,obs — reaction rate constant in the presence of the neutral salt; zA,
decrease in the potential value. At constant equilibrium potential for
DMAB (used in a large excess) it results in a lessening of the driving
force of the reaction.
However, such approach does not correspond strictly to a specific
shape of the curve k2,obs versus [Cl−]0. It is very similar to the monolayer
adsorption isotherm. It seems then that chloride ions can adsorb on the
particles and compete with AuCl4− and DMAB molecules in the adsorp-
tion on the catalytic gold surface. It inhibits the reaction, probably due
to electrostatic repulsion of chloride complex ions by adsorbed chloride
anions. Hence, an increase in the activation energy of the process was
observed. Shi and Lipkowski (1995) showed that adsorption of Cl−

Table 2
Parameters of the Arrhenius equation.

[AuCl4−]0, M Ea, kJ/mol A, s−1

−4
2.50 × 10 42.22 2.1 × 109
1.25 × 10−4 38.68 0.86 × 109
0.50 × 10−4 38.44 1.72 × 109
Fig. 11. Influence of temperature and chloride ions concentration on the rate constant.
Average 39.78 ± 2.11 1.56 × 109 ± 0.64 × 109
Experimental conditions: [AuCl4−]0 = 2.5 × 10−4 M, [DMAB]0 = 12.5 × 10−3 M.
 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53 49

Fig. 12. Influence of ionic strength on reaction rate constants. Experimental conditions: Fig. 13. The Arrhenius dependence for gold precipitation. Experimental conditions:
[AuCl4−]0 = 2.5 × 10−4 M, [DMAB]0 = 12.5 × 10−3 M, [Cl−]0 = 0.05 M, T = 298 K. [AuCl4−]0 = 2.5 × 10−4 M, [DMAB]0 = 12.5 × 10−3 M, [Cl−]0 = 0.05 M.

zB — charges of the reacting species; a — constant equaled to 0.509 for

aqueous systems at 298 K; I—– ionic strength of the solution; it is pos-
sible to calculate the charge of the reducing agent. In the studied case,
the charge of gold(III) chloride complex ions is known and is − 1. The
dependences described by Eq. (15) and calculated for various charges
of the reagents as well as for the AuCl4−–DMAB–NaClO4 system are
shown in Fig. 12.
Two dashed lines relates to the calculated results with the as-
sumption that reducing agent has either negative (− 1) or positive
(+ 1) charge, whereas dotted line corresponds to the case when the
reductant is in molecular (neutral) form. Square marks show the ex-
perimental results. Linear regression yields the slope equal − 0.25.
This value is close to 0, but simultaneously it is negative. It may sug-
gest that reductant is present in two forms as a molecule or as an
anion. However, linear dependence k2,obs on NaClO4 concentration
(i.e. ionic strength) presented in Fig. 10 is specific only for reactions
of ions with neutral molecules (Panczenkow and Lebiediew, 1964).
It seems that molecular DMAB acts as reductant.
3.2. Precipitation of solid phase
Precipitation of gold particles was monitored by turbidimetry.
Analysis of the experimental kinetic curves shows that Reaction (5)
is mainly responsible for the formation of the solid phase. It is
worth to note that at t = 0, there is no gold particles in the system,
but the presence of very small amount of the metallic nuclei produced
in the solution at very short times is enough to initiate the heteroge-
neous autocatalytic reaction. To describe Au particles formation
mathematical equation was fitted to the kinetic curves. Equation de-
scribing solely autocatalytic reaction (7) was adapted from the litera-
ture (Steinfeld et. al. 1989):
3.2.1. Activation energy of the process
Precipitation of gold particles was studied at various tempera-
tures. Using the Arrhenius equation, activation energy of the solid
phase precipitation was determined (Fig. 13). Values of k'2,obs were
calculated by fitting the Eq. (16) to the experimental kinetic curves.
The slope of the straight line was used for calculation of the activa-
tion energy. It was 43.99 kJ/mol. This value is close to that determined
in previous measurements. Moreover, similar value (42 kJ/mol) was
reported by Ohno (1991) for DMAB oxidation on Au electrode, but in
neutral solution. AuCl4− ions are reduced by DMAB directly to metal
in one three-electron step (Sadik et al., 2005) and the activation ener-
gies determined in two independent measurement series represent
the same values with measurement error.
3.2.2. Influence of initial DMAB concentration
The influence of the initial concentration of the reductant on
gold(0) precipitation rate was investigated. The experimental results
are presented in Fig. 14.
It is seen that the initial concentration of DMAB has a significant
influence on the rate constant of the solid phase precipitation. As it
was observed earlier, k’2,obs reached higher values for lower AuCl4−

h i
h i ½AuCl4 − 0 þ Au0
0
Au ¼ 0
ð16Þ
⋅eð½AuCl4 0 þ½Au 0 Þ⋅k2 t
½AuCl4 − 0  0
1þ
½Au0 0

According to the proposed model, it was calculated that for [AuCl4−]0 =

2.5 × 10 − 5 M, [Au o]0 is about 9 × 10 - 9 M. It is in an apparent contra-
diction with the real system, since methodology of the stopped flow
measurement should be also taken into account. During the tests
two solutions (AuCl4− and DMAB) are mixed in a T-shape micromixer
before spectrophotometric analysis of the mixture. It is enough time Fig. 14. Influence of initial DMAB concentration on rate constant of the gold precipita-
to initiate the “self-nucleation” in homogenous process. tion. Experimental conditions: [Cl−]0 = 0.05 M, T = 288 K.
50 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53

Fig. 15. Influence of the initial concentration of gold(III) ions on: a) rate constant, b) metal precipitation rate. Experimental conditions: [DMAB]0 = 12.5 × 10−3 M. [Cl−] = 0.05 M.

concentration. Contrary to the data presented in Fig. 6, k'2,obs is propor-
tional to the square root of the reductant concentration and k'2,obs ≈
k'2 ⋅ ε' ⋅ [DMAB] 0.5. It may point that in the studied system, reduction
proceeds by two paths at least. Similar to the plot in Fig. 6, the straight
lines do not intercept the origin of the coordinate system, but in this
case coevolution of the hydrogen bubbles can disturb the readings of
the apparatus.
3.2.3. Influence of gold(III) ions initial concentration
The influence of the initial concentration of gold(III) ions on metal
precipitation rate was also investigated. The results are shown in
Fig. 15 and Table 3. It was found that k'2,obs was inversely proportional
to gold(III) ions initial concentration (Fig. 15a), while a linear depen-
dence of v' on AuCl4− concentration in logarithmic coordination sys-
tem was found (Fig. 15b). It is in accordance to the data presented in
Figs. 7 and 8, where the influence of AuCl4− concentration on k2,obs
and v was shown, respectively.
It was assumed that equation describing the initial reaction rate v'
for the investigated process is:
0 0:5 − γ 0  γ
v ¼ k2 ⋅½DMAB0 ½AuCl4 0 ¼ k2;obs ⋅½AuCl4 0
where γ — the reaction order in respect to AuCl4; k'2,obs — rate con-
stant determined by fitting the Eq. (16) to the experimental kinetic
curves. Actual reaction order was then determined graphically. The
slopes of the lines were 1.44 and 1.43 for 288 K and 298 K, respec-
tively. Fractional values of the reaction order confirm that mecha-
nism of the process is complicated. Similar values obtained at two
temperatures confirm that one reaction (heterogeneous) dominates
in the system.
3.2.4. Microscopic analysis
Microscopic analysis of gold particles was done using STEM micro-
scope. Fig. 16a shows an exemplary image of the particles. It was
found that particles sizes are mainly in the range from 5 nm to
100 nm (Fig. 16b). Particles of various shapes (e.g. close to spherical or
polyhedral) were found in the sample. Single particles as well as parti-
cles' agglomerations were also observed. It is consistent with previous
observations and results obtained during registration of UV–VIS kinetic
spectra (Fig. 5), since the band at approximately 500–550 nm is usually
ascribed to the plasmon resonance of spherical gold particles, while
peak positions at longer wavelengths (600–900 nm) are determined
by the concentration of nonspherical nanoparticles (Link and El-Sayed,
1999). It is also generally accepted that the shape of the gold
nanoparticles is dependent on the adsorption ability of AuCl4− and Cl−
ions on various facets of the metallic seeds (Cao et al., 2006).
Single particle was analyzed using EBSD method. Fig. 17a shows a
view of examined area, whereas Fig. 17b presents Kikuchi patterns reg-
istered at point “1”. Distribution of the Kikuchi lines is characteristic for
ð17Þ the face centered cubic crystal lattice and corresponds to the metallic
gold crystal structure.
EDS analysis confirmed qualitative composition of the investigated
material. Spectra showed peaks characteristic for pure gold. The pres-
ence of copper as well as aluminum and oxygen was also detected,
but the peaks originated from the substrate and handle of the sample,
respectively.
4. Discussion

The obtained results show evidently that at ambient temperature

reduction of gold(III) complex ions with DMAB takes place and mecha-
nism of the process is rather sophisticated. One may suggest multifarious
Table 3
way of gold(III) chloride complex reduction. Process is initiated by ho-
Influence of the initial concentration of gold(III) ions on the precipitation rate. Experi-
mental conditions: [DMAB]0 = 12.5 × 10−3 M. mogenous reduction of AuCl4− Reaction (4) resulting in “self-nucleation”
of gold particles. In the presence of metallic particles, second (heteroge-
[AuCl4−]0, M log (v') k'2,obs s−1
neous) process immediately starts to occur Reaction (5). Precipitation of
288 K 298 K 288 K 298 K gold particles is accompanied by gaseous hydrogen evolution. It is also a
2.5 × 10-4 −1.71 −1.30 77.6 ± 0.7 199.6 ± 2.1 by-product of spontaneous decomposition of DMAB in acid solution and
1.25 × 10-4 −1.77 −1.50 135.5 ± 1.2 251.0 ± 12.2 can also act as a reducer of gold(III) complex ions.
5.0 × 10-5 −2.15 −1.78 143.0 ± 3.6 334.7 ± 3.5
2.5 × 10-5 −2.20 −1.88 253.0 ± 4.0 521.0 ± 3.5 ðCH3 Þ2 NHBH3 þ 4H2 O→ðCH3 Þ2 NH þ H3 BO4 þ 4H2 ð18Þ
 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53 51

Fig. 16. Microscopic image of gold nanoparticles (a) and particles' size distribution.

− − −
0
2AuCl4 þ 3H2 →2Au þ 6HCl þ 2Cl ð19Þ d½AuCl4   0
− ¼ k5 ⋅½AuCl4   ½Au   ½H2 O  ½ðCH3 Þ2 NHBH3  ð21Þ
dt
These four reactions may take place simultaneously.
d½H2   
Eqs. (4), (5), (18) and (19) were used to put down the following ¼ k18 ⋅ H2 O  ½ðCH3 Þ2 NHBH3 ð22Þ
set of differential equations: dt

−
d½AuCl4   d½AuCl4 −  
− ¼ k4 ⋅½AuCl4   ½H2 O  ½ðCH3 Þ2 NHBH3  ð20Þ − ¼ k19 ⋅½AuCl4   ½H2  ð23Þ
dt dt

Fig. 17. Results of gold nanoparticles analysis: a) micrograph, b) Kikuchi patterns, c) EDS spectrum.
52 M. Wojnicki et al. / Hydrometallurgy 127–128 (2012) 43–53

At large excess of the reducing agent and in the aqueous system ions (Ohno, 1991)). It is also possible that AuCl4− ions can compete
one can assume that concentrations of these components are con- in adsorption on gold nanoparticles surface, which corresponds to
stant. Then, the decrease in the experimental values of the rate constant.

k1;obs ¼ k1 ½H2 O  ½ðCH3 Þ2 NHBH3  ð24Þ

5. Conclusions
and
Dimethylamine borane is an effective reducing agent for gold(III)
k2;obs ¼ k2 ⋅½H2 O  ½ðCH3 Þ2 NHBH3  ð25Þ chloride complex ions at ambient temperature and in acidic aqueous
solution. The reduction may consist of two main paths, i.e.: reduction
Specific sigmoidal shapes of the kinetic curves show that reaction of gold(III) chloride complex ions by DMAB to metallic form in ho-
has mainly autocatalytic character. It is worth to note that Reaction mogenous and heterogeneous (autocatalytic) reactions. It seems
(4) accelerates Reaction (5) due to formation of new catalytic gold that gold(III) chloride ions are reduced in one step by direct electron
nuclei. However, we can assume that the rate of Reaction (4) is signif- transfer from DMAB to AuCl4−. The value of the activation energy for
icantly lower in comparison to heterogeneous process (5). Addition- the reaction is dependent on initial concentration of chloride ions
ally, despite that Process (19) is thermodynamically spontaneous, it and was found to be approx. 40 kJ/mol at [Cl −]0 = 0.05 M and
may be omitted in the considerations due to high stability of hydro- approx. 56 kJ/mol at [Cl −]0 = 1.05 M. Modification of initial concen-
gen molecules at ambient temperatures and under low pressure tration of Cl − ions has an inhibiting effect on reaction due to their ad-
(Agawam et al., 2006; Saarinen et al., 1998). Using these assumptions sorption on gold particles. Kinetic models for AuCl4− reduction were
the differential Eqs. (20)–(23) may be reduced to one Eq. (26): proposed and verified according to the experimental data. It was as-
sumed that the state of the catalytic surface of gold particles plays a
h i
d Au0 h i crucial role in the mechanism of the reaction and competition be-
−d½AuCl−  − 
tween strong AuCl4− adsorption and AuCl4− reduction on the metal
4 0
¼ ¼ k1;obs ½AuCl4  þ k2;obs AuCl4 ½Au
  
dt dt  
¼ k1;obs ½AuCl4  þ k2;obs ½AuCl4  ½AuCl4 0 ½AuCl4 Þ ð26Þ particles exists in the system.
DMAB can be used to recovery of gold form acidic aqueous solu-
and Eq. (26) can be transformed and solved to Eq. (9). tions. Its application leads to the metallic gold precipitation, initially
However, we can assume that the rate of reaction (4) is significantly in the colloidal form, but after about 24 hours it forms sediment easily
lower in comparison to heterogeneous process (Reaction (5)). Basing to filtration.
on the mass balance at any time of the process it may be written that:
h i Acknowledgments
 0  0
AuCl4  ¼ ½Au þ½AuCl4 0 ½Au  ð27Þ
0
This work was supported by the European Grant no. POIG.01.01.
and: 02.-00-015/09-00.

h i i The Authors thank Tomasz Tokarski, Ph.D., from Department of
d½AuCl4 −  0  0  
− ¼ k5 ⋅½AuCl4   Au þ½AuCl4  ½AuCl4 Þ ð28Þ Structure and Mechanics of Solids at Faculty of Non-Ferrous Metals
dt 0 0
of AGH University of Science and Technology for his help during
It can be solved using variable separation method: STEM analysis.

½AuCl4 − 
d½AuCl4− 
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