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ABSTRACT

Bromine is a potential reagent in gold extractive


metallurgy. The reaction kinetics of the adsorption of
gold on activated kinetic is studied. Solution pH is
found to have little effect at pH ≤ 6. At high pH levels,
pH is found to inhibit the reaction strongly. Particle
size is found to be inversely proportional to reaction
Adsorption of Gold on rate, as predicted by our reaction model. Bromine is
found to strongly inhibit the reaction. It is found that
Activated Carbon the reaction rate is inversely proportional to bromine
concentration. The reaction rate is found to be first
order with respect to carbon amount. Temperature is
found to have little effect on reaction rate. The
activation energy is found to be 2.66 kcal/mol.

Chancler Vander Woude


MSE 413: Phase Transformation and Kinetics

T
MSE 413 Chancler Vander Woude 1

1 INTRODUCTION
Since 1887, cyanide has been used as the primary reagent for extraction of gold, using the MacArthur-
Forrest process [1]. However, cyanide is highly toxic and widespread public disapproval mandates that a
replacement reagent be found. Bromine is one such candidate, as it has the potential to outperform
cyanide in kinetics, toxicity, and operating costs [2].
(Eq 1) 𝐴𝑢 + 𝐵𝑟2 + 2𝐵𝑟 − → 𝐴𝑢𝐵𝑟4−

Bromine reacts with gold according to Equation 1. The resulting tetrabromoaurate is water soluble
allowing bromine to leach gold from gold ores. Several methods of extracting the gold from the
tetrabromoaurate exist. Among these are electrowinning processes, chemical precipitation, and
adsorption of gold on activated carbon. It is known that the adsorption of gold on activated carbon is
first order with respect to concentration of gold. Thus:
𝑑𝐶𝐴𝑢𝐵𝑟4 𝐷𝐴
(Eq 2) =− 𝐶
𝑑𝑡 𝑉𝛿 𝐴𝑢𝐵𝑟4
Where D is a diffusion coefficient (cm2/sec), A is the surface area (cm2), V is a solution volume (cm3),  is
the thickness of a diffusion film layer (cm), and 𝐶𝐴𝑢𝐵𝑟4 is a concentration of the adsorbent (mole/cm3).
Assuming spherical particles, the surface area of a particle is a function of particle size squared, the total
surface area is product of the surface area of a particle and the number of particles, the number of
particles is the mass of carbon divided by the density and volume of a particle. With this information we
can derive the following relation:
3𝐷𝑔 1
(Eq 3) ln(𝐶𝐴𝑢𝐵𝑟4 ) = − ∗ 𝑡
𝑉𝛿𝜌 𝑟𝑜

Where g is the carbon’s mass, and  is the density of the carbon.

The objective of this study is to familiarize the students with the lab equipment and to examine the
reaction kinetics of adsorption of gold on activated carbon. This is accomplished using an atomic
absorption spectrometer to measure the gold concentration of the gold-bromine solution at regular
intervals. Using Equation 3, we can find the rate constant by linear regression of ln(𝐶𝐴𝑢𝐵𝑟4 ) versus time.
Using the rate constant, we study the effects of solution pH, particle size, bromine concentration,
amount of carbon, and temperature on the adsorption of gold on activated carbon.

In this study we examine the effects of concentration of a species to find the reaction order with respect
to that species. We use concentration to find reaction order by taking the natural log of the generic
reaction rate equation:

𝑟 = 𝐷𝑐 𝑛 ln(𝑟) = ln(𝐷) + 𝑛 ∗ ln(𝑐)


Since the rate constant is proportional to the rate, the slope of the log of the rate constant versus log of
concentration will be the reactions order.

Similarly, we use temperature to find activation energy by taking the natural log of the Arrhenius equation:
𝑄 1 𝑄 1
D = 𝛾𝑒 −𝑅 ∗𝑇 𝑙n(𝐷) = ln(𝛾) − ∗
𝑅 𝑇
MSE 413 Chancler Vander Woude 2

Since the rate constant is proportional to D, the slope of the log of the correct model’s slopes versus the
inverse of temperature will be related to activation energy in the following equation, where m is the slope:

𝑄 = −𝑅 ∗ 𝑚
In order to give the students, the opportunity to familiarize themselves with the equipment a lab is
performed. However, due to inexperience and experimental error their data isn’t conducive to analysis.
Data provided by Dr. Batric Pesic is used in its place.

2 PROCEDURE
100 mL of AuBr solutions with 5mg/l Au concentration are prepared. Solutions are placed in the reactor
vessel with the temperature set to 25oC. The vessel has a temperature controlled water bath, stirred at a
high rate to ensure even temperature. 100mg of carbon (10x14 mesh) is added to the solution. The
solution is stirred using a stir bar at a rate of 600 rpm. 500 L samples are taken from the solution using
a micropipette at 0, 3, 10, 20, 40, 60, 90 and 180 minutes.

These samples are then analyzed for gold content using an atomic absorption spectrometer.

3 RESULTS
The natural log of gold concentration is found to be linear with respect to time, as predicted by Equation
3. At very low concentrations (<0.5 mg/L) this does not hold true. This effect is attributed to the
resolution of the atomic absorption spectrometer at low concentrations. Non-linear data with low gold
concentrations are excluded.

3.1 EFFECT OF PH

Figure 1: Gold adsorption on activated carbon at varied solution Figure 2:Effect of solution pH on gold absorption kinetics
pH

The effect of solution pH on gold adsorption rate is seen in Figure 2. pH shows negligible effect on the
reaction rate at pH ≤ 6. At high pH levels the reaction rate is slowed dramatically.
MSE 413 Chancler Vander Woude 3

3.2 EFFECT OF PARTICLE SIZE

Figure 3: Gold adsorption on activated carbon of varied particle mesh size Figure 4: Effect of particle size on gold adsorption rate

The rate constant is linear with respect to inverse particle size, with an R2 of 0.9919. This is as predicted
by Equation 3.

3.3 EFFECT OF BROMINE CONCENTRATION

Figure 5: Gold adsorption on activated carbon in the presence of bromine Figure 6:Effect of Bromine concentration on gold adsorption rate

Bromine was found to strongly inhibit


gold adsorption rate on activated
carbon. Evidence suggests that
reaction rate is inversely proportional
to bromine concentration

3.4 EFFECT OF CARBON AMOUNT


The effect of carbon amount on the
reaction rate was found to be linear
with respect to amount carbon (seen
in Figure 8), indicating a first order
reaction. Figure 7: Gold adsorption on activated carbon of varied amounts
MSE 413 Chancler Vander Woude 4

Figure 9: Gold adsorption on activated carbon at varied temperature


Figure 8: Effect of amount of carbon on adsorption of gold

3.5 EFFECT OF TEMPERATURE


The effect of temperature on the absorbance of
gold was found to be very small. Activation energy
is determined to be 2.66 kcal/mol.

4 CONCLUSION
Figure 10: Arrhenius plot of the adsorption of gold on activated
This study analyzed the kinetics of the adsorption
carbon
of gold on activated carbon. It studied the effects
of solution pH, particle size, bromine concentration, amount of carbon, and temperature on the
reactions kinetic. Solution pH is found to have little effect at pH ≤ 6. At high pH levels, pH is found to
inhibit the reaction strongly. Particle size is found to be inversely proportional to reaction rate, as
predicted by our reaction model. Bromine is found to strongly inhibit the reaction. It is found that the
reaction rate is inversely proportional to bromine concentration. The reaction rate is found to be first
order with respect to carbon amount. Temperature is found to have little effect on reaction rate. The
activation energy is found to be 2.66 kcal/mol, indicating that the reaction is diffusion controlled.

5 REFERENCES
1. Vella, Heidi. “Should Cyanide Still Be Used in Modern-Day Mining?” Mining Technology, Kable, 7
Mar. 2016, www.mining-technology.com/features/featureshould-cyanide-still-be-used-in-
modern-day-mining-4809245/.
2. Pesic, Batric, and Victor C. Storhok. “Adsorption of Gold on Activated Carbon in Bromide
Solutions.” Metallurgical Transactions B, vol. 23, no. 5, 1992, pp. 557–566.,
doi:10.1007/bf02649715.

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