LAURENTIAN UNIVERSITY

UNIVERSITÉ LAURENTIENNE

Date: April 12, 2003 Course No. ENGR 3226 E

Total No. of Pages: 6 Questions: 5
Professor: H. Shang Time allowed: 3 hours

. USE OF CALCULATERS AND ONE-PAGE FORMULA SHEET IS PERMITTED.

NO OTHER AIDS ALLOWED.

1. (25%) Thermodynamic data for the Au-SCN-H2O system are provided in the
attached potential –pH diagram for the system. In addition, values of Gibbs free
energy are presented in tabular form for selected species. Based on these data:

a) Determine the dissociation constant for thiocyanic acid and dram the line
representing the equilibrium on the Eh – pH diagram. The dissociation of
thiocyanic acid is given by the equation

HSCN = H+ + SCN-

b) Write the chemical equations for the equilibrium represented by lines 37,
56, 60 and 61 on the Pourbaix diagram.
c) Determine the Eh –pH relationship corresponding to the equilibrium
represented by line 60.
d) Cyanic acid (HCNO), a weak acid (pK=3.9), is metastable in water at 25
o
C. It can be produced by the oxidation of aqueous thiocyanic acid
solutions. Write chemical equations representing the oxidation of the
thiocyanides (HSCN and SNC-) to cyanates (HCNO and CNO-). State the
pH range for which each of the equations is valid.
2. (10%) A reaction occurring at an interface has an activation energy of 100 kJ/mol.
Would the rate of this reaction be increased more by an increase in temperature from 80
o
C to 90 oC or by an extension of its effective interfacial surface area by a factor of 2?

3. (10%) The dissolution of cobalt metal in ammoniacal solutions can be described by the
following equation

3 3
Co + O2 + 6 NH 3 + H 2 O = Co( NH 3 ) 36+ + 3OH −
4 2

Using the electrochemical theory as a model for the leaching process, derive a rate
equation describing the rate of dissolution of cobalt.

With respect to the anodic reaction you may make the following assumptions:

a) The reaction is Co + N H3 = Co(NH3)3+ + 3e-

b) The rate of the chemical reaction between Co and ammonia is rate controlling, all
diffusional steps involved are fast.
c) The addition of other ammonia molecules to the initial reaction product,
Co(NH3)3+ occurs in the bulk phase.

State clearly for any assumption you make regarding the cathodic reaction.
4. (20%) A counter current ion exchange column removes copper ions (Cu+2) from a
wastewater stream. The copper ion concentration is 350 mg/l and there is 99.9 percent
removal. The wastewater has a flow upwards of 3.0 l/s-m2 and the ion exchange resin
flows downwards. The ion exchange capacity of the resin is 4.50 meq/g and the resin
flow leaving the column is saturated with copper ions ( that is, essentially all the
exchange sites are occupied by copper ions)

Molecular weight of Cu = 63.54 meq = mili equivalents

Determine:

a) The resin mass flow rate, kg/h-m2

b) The litres of wastewater treated by 1 kilogram of resin
c) The diameter of the column in meters if the flow rate is 6.3 l/s
d) If the column height is 3.6m and the voidage of the fluidized bed is 75%, what is
the mean liquid residence time?
5. (15%) Nickel is to be stripped from a 15% solution of D2EHPA in Solvesso 150 by a
strip liquor containing 35g/l nickel. The entering solvent stream contains 3 g/l nickel and
the pregnant strip liquor which serves as a feed to an electrowinning plant must contain
60g/l Ni.

Determine the number of theoretical stages required and the organic to aqueous phase
ratio necessary if 90% of the nickel is to be stripped from the loaded solvent during this
operation. Data for this process, in the form of an equilibrium isotherm at 20 oC, are
provided below.
6. (20%) A copper refinery operates with 50 cathodes and 49 anodes per tank. When
operating at 22,000 amps/tank, a cell voltage of 250 mv and a current efficiency of 93%
determine:

a) The rate of cathode growth (kg/day).

b) The power cost ($/ton of cathode copper) if the cost of AC electrical energy is
purchased at $0.095 /(kw.hr), and the rectifier you use to convert it to DC power
operates at an efficiency of 88%.

c) The cathode current density if the cathodes are 0.9m*0.9m