MTRL 358 - Major Assign #1 - SOLUTIONS - Winter 2023 T1

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Assignment 1, 2023 - Chemistry review and Hydrometallurgical Chemistry 1. In any process chemical industry, including hydrometallurgy, it is important to gain an understanding of the periodic table. This question begins to address that. Match the compound or element on the right to the definition or term on the left. There will be one unique compound/element per term or definition. By process of elimination determine the most suitable match for each phrase. Strong acid H 2 SO 4 The most electronegative metal Au Main group metal Pb Strong oxidant Cl 2 Most important industrial base CaO Strong base NaOH Strong reducing agent Na Transition metal Ti Strong electrolyte NaCl Strongly sulphophilic metal Fe Amphoteric ion HSO 3 - Weak acid H 2 S Semi-metal As Incorrect chemical formula NaCO 3 2. Fill in the blanks: (a) In an electron transfer reaction when an oxidizing agent reacts it gets reduced . (b) Reduction is gain of electrons. (c) A reducing agent loses electrons. (d) What is the term we use for -log 10 [H + ]? pH (e) A salt is a compound composed of ions . 3. Select the most comprehensive and correct definition for a base in aqueous solution. A base is a compound that (a) has an ionizable OH - group and raises the pH. (b) has an ionizable OH - group and lowers the pH. Faculty of Applied Sciences Department of Materials Engineering MTRL 358: Hydrometallurgy I Assignment #1 – SOLUTIONS
(c) accepts a proton and raises the pH . (d) accepts a proton and lowers the pH. 4. Which of the following compounds (a) will act as an acid in water: CH 4 , CO 2 , HCO 3 - , HNO 3 , NH 3 (b) will acts as a base in water: HCO 3 - , SO 4 2- , NaCH 3 CO 2 , N 2 , C 6 H 5 OH (phenol) 5. Answer the following questions: (a) Why is the chemical formula Mg 2 PO 4 incorrect? PO 4 3- has a 3- charge; Mg +2 has a +2 charge. To form a balanced compound the simplest formula must be Mg 3 (PO 4 ) 2 . (b) What is the formula for the highest possible oxide of titanium? Ti is a group IVa element. It can form up to 4 electron-pair bonds. Oxygen is a group VIb element. It can form 2 electron pair bonds by gaining two electrons. Hence the highest oxide of Ti is TiO2. The 2 O atoms each gain 2 electrons from Ti (formally) and the Ti shares (loses, formally) 4 electrons. (c) What is the value of n in the formula: H 3 AsO n where As forms the maximum number of electron pair bonds possible? (The H atoms are bound to oxygens.) Briefly explain your answer. As is a group Vb element. It will form 5 electron pair bonds. Each O forms two electron pair bonds. Since there are three H atoms are bound to O atoms, the groups are –OH where one electron pair bond still can form between O and As. This gives As-(OH) 3 . But this would leave As as only trivalent. Hence one more O atom forms two electron pair bonds with As, i.e. (HO) 3 As=O. Each O is divalent; the As is pentavalent. The formula is H 3 AsO 4 . 6. Indicate which of the following are soluble salts in water: HCl, Ag 2 S, Na 2 S , C 12 H 22 O 11 (sugar), S 8 , NH 3 , CuO, PbCl 2 , CaO, CO 2 , H 2 , Te Only Na 2 S. Note that HCl, C 12 H 22 O 11 and NH 3 are all soluble, but, not salts. S 8 , H 2 , CO 2 and Te are not salts and not soluble. Ag 2 S, CuO, PbCl 2 and CaO are insoluble salts. 7. Perform the required calculations for the following aqueous solutions: (a) Calculate the pH of a solution made up of 5.00 mL of 1.2 M HCl diluted to precisely 250 mL. 5 x 1.2 M H + /250 = 0.024 M H + (HCl is a strong acid; fully dissociates.) pH = -log 10 (0.024) = 1.62 (b) A solution contains a total ammonia concentration of 0.8 M (the sum of ammonia and ammonium concentrations). The volume is 1.5 L and the pH is 9.6. What volume (mL) of aqueous ammonia (density =
0.90 g/mL and 28% by mass, i.e. 280 g NH 3 /kg of solution) and mass of ammonium sulfate (in g) were added to make up the solution? Use K b for ammonia = 1.8 x 10 -5 . [NH 3 ] + [NH 4 + ] = 0.8 pH = pK a + log([NH 3 ]/[NH 4 + ]) = 9.6 K a = 1 x 10 -14 /1.8 x 10 -5 = 5.556 x 10 -10 pK a = 9.2553 9.6 = 9.2553 + log([NH 3 ]/[NH 4 + ]) 10 0.3447 = 2.212 = [NH 3 ]/[NH 4 + ] [NH 3 ] = 2.212[NH 4 + ] 2.212[NH 4 + ] + [NH 4 + ] = 0.8 = 3.212[NH 4+ ] [NH 4 + ] = 0.2491 M [NH 3 ] = 0.5509 M moles NH 4 + = 1.5 L x 0.2491 mol/L = 0.37365 mol There are two moles of NH 4 + per mole (NH 4 ) 2 SO 4 , so we need 0.37365/2 mol (NH 4 ) 2 SO 4 , or 132.136 g/mol x 0.37365/2 = 24.69 g . 1L of aqueous ammonia weighs 900 g. 28% of this is NH 3 , i.e. 252 g NH 3 . 252 g NH 3 /17.031 g NH 3 /mol NH 3 = 14.797 mol/L The volume needed is 1.5 L solution x 0.5509 mol NH 3 /L/14.797 mol NH 3 /L = 0.0558 L = 55.8 mL (c) An acetic acid solution has a pH of 2.78. What concentration of the acetic acid (in molar) was added to make up the solution? Take K a for acetic acid to be 1.75 x 10 -5 . Acetic acid has the formula CH 3 CO 2 H. HA = H + + A - K a Co – x x x M (Let x = [H + ] = [A - ] at equilibrium) x 2 /(Co - x) = K a x 2 /K a + x = Co
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x = 10 -2.78 = 0.0016596 Co = 0.159 M = [acetic acid] added (d) Estimate the pH of a solution that contains 0.5 M nickel sulfate and solid NiO. (Look up the necessary data in the Chemistry Review Part II notes.) NiO + H 2 O = Ni +2 + 2OH - K sp = 1.6 x 10 -16 Since K sp << 1 and [NiSO 4 ] is relatively high, at equilibrium [Ni +2 ] is very nearly 0.5 M. K sp = [Ni +2 ][OH - ] 2 = 0.5[OH - ] 2 = 1.6 x 10 -16 [OH - ] = 1.7889 x 10 -8 M [H + ] = 1 x 10 -14 /1.7889 x 10 -8 = 5.5902 x 10 -7 M pH = -log 10 (5.5902 x 10 -7 ) = 6.25 8. The solubility of many metal oxides is enhanced by complexation. Ammonia is an example of a complexing agent that finds some use in hydrometallurgy. Nickel leaching from various minerals is practiced using ammonia as a complexing agent. Some relevant data are given below: (Show your work; no marks with work shown.) Ni(OH) 2 K sp = 6 x 10 -16 logK n for [Ni(NH 3 ) n ] +2 : NH 4 + K a = 5.75 x 10 -10 K w = 1 x 10 -14 (i) What is the solubility of Ni(OH) 2 in water alone? (Express your answer in g Ni/L.) Ni(OH) 2 = Ni +2 + 2OH - K sp = [Ni +2 ][OH - ] 2 Let x = [Ni +2 ]; then 2x = [OH - ] K sp = x(2x) 2 = 6 x 10 -16 n = 1 2 3 4 5 2.36 1.90 1.55 1.23 0.85
x = 5.313 x 10 -6 M [Ni +2 ] = 5.313 x 10 -6 mol/L x 58.6934 g/mol = 3.12 x 10 -4 g Ni +2 /L (ii) The reaction below depicts leaching of Ni(OH) 2 in ammonia solution to form [Ni(NH 3 ) 5 ] +2 : Ni(OH) 2 + 5NH 3 = [Ni(NH 3 ) 5 ] +2 + 2OH - Determine the equilibrium constant for the reaction. Ni(OH) 2 = Ni +2 + 2OH - K sp Ni +2 + 5NH 3 = [Ni(NH 3 ) 5 ] +2 β 5 The sum of the two reactions is the overall reaction above; K = K sp β 5 . log β 5 = logK n = 7.89 5 n=1 (alternatively β 5 = K n 5 n=1 where K n = 10 logK n ) β 5 = 7.762 x 10 7 K = 6.762 x 10 7 x 6 x 10 -16 = 4.6575 x 10 -8 (iii) What is the solubility of Ni(OH) 2 in 1 M aqueous ammonia solution (in g Ni/L)? Assume that only the [Ni(NH 3 ) 5 ] +2 complex forms. (This is a significant over-simplification, but it will serve to illustrate the point*.) Let x = [Ni +2 ] at equilibrium (as the Ni +2 -NH 3 complex); other concentrations then are as shown below: Ni(OH) 2 + 5NH 3 = [Ni(NH 3 ) 5 ] +2 + 2OH - 1 - 5x x 2x based on the reaction stoichiometry K sp = x(2x) 2 (1 5x) 5 = 4.657 × 10 −8 Solving for x is best done with approximate methods, such as used by Solver in Excel. x = 0.0022246 M [Ni +2 ] = 0.0022246 x 58.6934 = 0.131 g Ni +2 /L This is a great improvement over solubility of Ni(OH) 2 in water alone, but still quite low. (iv) Add a suitable multiple of the ammonia base dissociation reaction to the reaction in part (ii) to obtain a reaction that converts all the OH - to NH 3 . (Just enough NH 4 + to react with all the OH - .) Determine the equilibrium constant for the reaction.
Ni(OH) 2 + 5NH 3 = [Ni(NH 3 ) 5 ] +2 + 2OH - This requires 2 NH 4 + to consume the OH - : 2NH 4 + + 2OH - = 2NH 3 + 2H 2 O K = 1/K b 2 = K a 2 /K w 2 Ni(OH) 2 + 2NH 4 + + 3NH 3 = [Ni(NH 3 ) 5 ] +2 + 2H 2 O K = 4.657 x 10 -8 x (5.75 x 10 -10 ) 2 /(1 x 10 -14 ) 2 = 154.0 (v) What is the solubility of Ni(OH) 2 in an ammonia solution with a total ammonia concentration of 1 M ([NH 3 ] + [NH 4 + ] = 1) where [NH 4 + ]/[NH 3 ] = 2/3 (as per the reaction)? [NH 3 ] o = 0.6 M; [NH 4 + ] o = 0.4 M Ni(OH) 2 + 2NH 4 + + 3NH 3 = [Ni(NH 3 ) 5 ] +2 + 2H 2 O Let x = [Ni +2 ] at equilibrium 0.4 - 2x 0.6 - 3x x K = x (0.4 2x) 2 (0.6 3x) 3 = 154 x = 0.10823 M [Ni +2 ] = 0.10823 x 58.6934 = 6.35 g/L This is greater than Ni(OH) 2 solubility when ammonia alone is used. The ratio of 2:3 ratio of [NH 4 + ]:[NH 3 ] gives the maximum solubility of Ni(OH) 2 in ammonia-ammonium solution. Just enough NH 4 + is used in the reaction to consume all the OH - that is released. If there is more NH 4 + then there is less NH 3 to complex Ni +2 . More NH 3 and there is not enough NH 4 + to react with the OH - released. Either way the solubility of Ni(OH) 2 declines. *There is actually much more at play here. There is also a [Ni(NH 3 ) 6 ] +2 complex, though its formation constant is relatively small. However, each [Ni(NH 3 ) n ] +2 complex will contribute to the total nickel dissolved. The approximation that the only complex contributing to dissolution of Ni(OH) 2 is the [Ni(NH 3 ) 5 ] +2 is imperfect. However, it does demonstrate what is going on, and gives a decent first-order estimate of the effect. Although it takes a bit more effort to get a more accurate picture, the methodology is not difficult.
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