Practice problems
Answer key at the back. Work in the units each problem states.
Thermochemistry
1. Heat in the cup — A calorimetry class heats 200 g of water in an open cup from 18.0 °C to 43.0 °C. Take the specific heat capacity of water as 4.18 J/(g·°C). Calculate the heat absorbed by the water.
2. Heat in the cup — A 250 g portion of hot water is left in a coffee-cup calorimeter and cools from 72.0 °C to 62.0 °C. Take the specific heat capacity of water as 4.18 J/(g·°C). Calculate the heat change of the water, sign included.
3. Warming and melting — A 20 g block of ice sits at 0 °C in an insulated flask. Heat is supplied until the last of it has just melted, with the mixture still at 0 °C. For water, the latent heat of fusion is 334 J/g and the latent heat of vaporization is 2260 J/g. Calculate the heat required to melt the ice.
4. Warming and melting — On the same heating curve, 250 g of liquid water is warmed by 10 C° along the slope between the two plateaus. Take c = 4.18 J/(g·°C); for water the latent heat of fusion is 334 J/g. Calculate the heat absorbed along that slope.
5. Heat per mole — A 64.0 g sample of methanol (CH₃OH, M = 32.0 g/mol) is burned completely. Its molar enthalpy of combustion is -726 kJ/mol. Calculate the heat change for the sample, sign included.
6. Heat per mole — A 92.0 g sample of ethanol (C₂H₅OH, M = 46.0 g/mol) is burned completely. Its molar enthalpy of combustion is -1367 kJ/mol. Calculate the heat change for the sample, sign included.
7. The coffee cup — In a coffee-cup calorimeter, 50.0 mL of 1.00 mol/L hydrochloric acid is mixed with 50.0 mL of 1.00 mol/L sodium hydroxide, both starting at the same temperature. The mixture warms by 7.2 C°. Treat the combined solution as 100 g of water with c = 4.18 J/(g·°C), and assume the calorimeter itself absorbs no heat. Determine the molar enthalpy of neutralization, per mole of acid.
8. The coffee cup — In a coffee-cup calorimeter, 200.0 mL of 0.50 mol/L copper(II) sulfate solution is stirred with an excess of zinc powder. The solution warms by 24.0 C°. Treat the solution as 200 g of water with c = 4.18 J/(g·°C), and assume the calorimeter itself absorbs no heat. Determine the molar enthalpy of reaction, per mole of copper(II) ion.
9. The ladder of Hess — A data sheet gives three reactions bearing on the formation of ethene. Step 1: C(s) + O₂(g) → CO₂(g), ΔH = -394 kJ/mol. Step 2: H₂(g) + ½ O₂(g) → H₂O(l), ΔH = -286 kJ/mol. Step 3: C₂H₄(g) + 3 O₂(g) → 2 CO₂(g) + 2 H₂O(l), ΔH = -1411 kJ/mol. The target reaction is 2 C(s) + 2 H₂(g) → C₂H₄(g). Each step may be reversed, or multiplied through, before the sum is taken. Determine the enthalpy change of the target reaction.
10. The ladder of Hess — A data sheet gives three reactions bearing on the formation of acetylene. Step 1: C(s) + O₂(g) → CO₂(g), ΔH = -394 kJ/mol. Step 2: H₂(g) + ½ O₂(g) → H₂O(l), ΔH = -286 kJ/mol. Step 3: C₂H₂(g) + 5/2 O₂(g) → 2 CO₂(g) + H₂O(l), ΔH = -1300 kJ/mol. The target reaction is 2 C(s) + H₂(g) → C₂H₂(g). Each step may be reversed, or multiplied through, before the sum is taken. Determine the enthalpy change of the target reaction.
11. The formation shortcut — A standard thermochemistry table is used to evaluate the balanced reaction CaCO₃(s) → CaO(s) + CO₂(g). The table lists ΔH°f(CaO(s)) = -635 kJ/mol; ΔH°f(CO₂(g)) = -394 kJ/mol; ΔH°f(CaCO₃(s)) = -1207 kJ/mol. All values are quoted at 25 °C and 100 kPa. Determine the standard enthalpy change of the reaction.
12. The formation shortcut — A standard thermochemistry table is used to evaluate the balanced reaction 2 SO₂(g) + O₂(g) → 2 SO₃(g). The table lists ΔH°f(SO₃(g)) = -396 kJ/mol; ΔH°f(SO₂(g)) = -297 kJ/mol. It prints no entry at all for an element in its standard state. All values are quoted at 25 °C and 100 kPa. Determine the standard enthalpy change of the reaction.
13. The Heat Audit — End of shift in the calibration lab. A 5.0 g pellet of fuel X (M = 20.0 g/mol) is burned completely in a calorimeter holding 500 g of water. The molar enthalpy of combustion of X is −210 kJ/mol, all of the heat reaches the water, and today c = 4.2 J/(g·°C) because the calculator is locked in the drawer. The protocol only signs off on the run if the water's temperature rise reaches at least 30 C°. Work each line — every answer feeds the next. Determine whether this run meets the protocol's temperature-rise specification.
14. The Heat Audit — Bonus mark, no calculator. A route to a target reaction runs through three tabulated steps: ΔH₁ = -400 kJ/mol, ΔH₂ = -300 kJ/mol, ΔH₃ = -1600 kJ/mol. Step 1 must be doubled, step 2 must be doubled, and step 3 must be reversed. Determine the enthalpy change of the target reaction.
Rates & Kinetics
15. Arrhenius and the hill — A kinetics table lists a first-order reaction with A = 1.0 × 10¹⁴ s⁻¹ and Ea = 80.0 kJ/mol. A technician runs it in a thermostatted bath at 127 °C. Calculate the rate constant at that temperature.
16. Arrhenius and the hill — A kinetics table lists a first-order reaction with A = 1.0 × 10¹⁴ s⁻¹ and Ea = 80.0 kJ/mol. A technician runs it in a thermostatted bath at 127 °C. Calculate the rate constant at that temperature.
17. Two temperatures — The same reaction is timed twice. At 27 °C its rate constant is 2.0 × 10⁻³ s⁻¹; at 37 °C the same reaction returns 4.0 × 10⁻³ s⁻¹. Subscript 1 is the cooler run, subscript 2 the warmer one. Determine the activation energy of the reaction, in kJ/mol.
18. Two temperatures — A class measures the rate constant of one reaction at five temperatures, plots ln k against 1/T, and finds the points fall on a straight line of slope −5.00 × 10³ K. Calculate the activation energy from the slope, in kJ/mol.
19. Straight-line decay — A decomposition running on a fully saturated catalyst surface — every site busy, so the rate never changes — a zero-order reaction. It starts at 1.20 mol/L with a rate constant of 0.0100 mol/(L·s), and runs undisturbed for 30.0 s. Calculate the concentration of reactant remaining.
20. Straight-line decay — A dissolved drug clears the bloodstream by a first-order route, with a rate constant of 0.0462 s⁻¹. The sample begins at 0.800 mol/L and is left for 30.0 s. Determine the concentration remaining at that time.
21. The half-life clock — A radiolabelled compound in a shielded vial decays by a first-order process with a rate constant of 0.0578 s⁻¹. Calculate the half-life of the sample.
22. The half-life clock — An isotope tracer in a hospital's hot lab is observed to lose exactly half of its reactant every 10.0 s. Determine the first-order rate constant.
23. Second-order slowdown — Two NO₂ molecules must meet for this decomposition to happen at all, which makes it second order. It begins at 0.100 mol/L with a rate constant of 0.150 L/(mol·s), and is followed for 100 s. Calculate the concentration remaining.
24. Second-order slowdown — A second-order dimerization has a rate constant of 0.500 L/(mol·s). A run is charged at 0.0400 mol/L. Determine the half-life of this run.
25. The Rate Tribunal — The last batch of the shift. A reactant decomposes by a first-order route. At 300 K the plant logs an initial rate of 0.050 mol/(L·s) with the tank charged at 5.0 mol/L. The operator then warms the tank to 310 K — ten degrees, and this reaction is one of the well-behaved ones whose rate constant DOUBLES over that step — and holds it there for 105 s. Plant rules: the batch may be discharged only once less than 10 % of the original reactant is left. No calculator, and today ln 2 = 0.70. Work each line — every answer feeds the next. Determine whether this batch may be discharged, one line at a time.
26. The Rate Tribunal — Bonus mark, still no calculator. On a separate bench trial the technician doubles the concentration of A, holds the temperature, and watches the initial rate rise by a factor of 4. Determine the order in A, then predict what tripling the concentration would do.
Chemical Equilibrium
27. Writing K — A sealed vessel holds the one-to-one gas equilibrium A(g) + B(g) ⇌ C(g) + D(g). At equilibrium the concentrations measure [A] = 0.10 M, [B] = 0.20 M, [C] = 0.40 M and [D] = 0.40 M. Determine the equilibrium constant Kc for the reaction as written.
28. Writing K — In an industrial water-gas shift reactor, carbon monoxide and steam settle into equilibrium with carbon dioxide and hydrogen: CO(g) + H₂O(g) ⇌ CO₂(g) + H₂(g). At 700 K the equilibrium concentrations are [CO] = 0.20 M, [H₂O] = 0.20 M, [CO₂] = 0.20 M and [H₂] = 0.60 M. Calculate the equilibrium constant Kc at this temperature.
29. Q against K — At 700 K the water-gas shift CO(g) + H₂O(g) ⇌ CO₂(g) + H₂(g) has Kc = 60. A sample drawn from a running reactor contains [CO] = 0.40 M, [H₂O] = 0.20 M, [CO₂] = 0.80 M and [H₂] = 0.50 M. Calculate the reaction quotient, and state which way the mixture will shift.
30. Q against K — Inside a Haber converter, N₂(g) + 3H₂(g) ⇌ 2NH₃(g) has Kc = 0.060 at the operating temperature. A sample valve is opened mid-run and the mixture reads [N₂] = 0.50 M, [H₂] = 0.20 M and [NH₃] = 0.10 M. Calculate the reaction quotient, and state which way the converter is running.
31. Kp meets Kc — Ammonia is cracked over a hot catalyst to feed a hydrogen line: 2NH₃(g) ⇌ N₂(g) + 3H₂(g). Before Kp and Kc can be compared, the exponent on (RT) has to be settled. Determine Δn for this reaction as written.
32. Kp meets Kc — A sealed tube of colourless dinitrogen tetroxide is warmed until it browns: N₂O₄(g) ⇌ 2NO₂(g). At 300 K the concentration equilibrium constant is Kc = 5.0, and Δn for this reaction is +1. Take R = 0.0821 L·atm/(mol·K). Calculate the pressure equilibrium constant Kp at this temperature.
33. Sparingly soluble — At 25 °C, calcium fluoride (CaF₂) has a solubility product of 3.2 × 10⁻¹¹. Each formula unit releases three ions — two of one, one of the other. Determine the molar solubility of the salt.
34. Sparingly soluble — A saturated solution of magnesium hydroxide (Mg(OH)₂) at 25 °C holds 1.0 × 10⁻⁴ mol/L of dissolved salt. Each formula unit releases three ions — two of one, one of the other. Calculate the solubility product of the salt.
35. Gibbs decides — For the decomposition N₂O₄(g) ⇌ 2NO₂(g), tables give ΔH° = +57 kJ/mol and ΔS° = +176 J/(mol·K). The reaction is run at 298 K. Calculate ΔG° at this temperature, and state whether the reaction is spontaneous.
36. Gibbs decides — For the thermal cracking of a hydrocarbon feed, ΔH° = +150 kJ/mol and ΔS° = +200 J/(mol·K). Both are taken as temperature-independent. Somewhere on the temperature scale ΔG° passes through zero and the reaction changes its mind. Determine the temperature at which ΔG° equals zero.
37. The Position of Equilibrium — Final examination, contact-process unit. In a converter at 300 K, 2SO₂(g) + O₂(g) ⇌ 2SO₃(g) reaches equilibrium with [SO₃] = 0.20 M, [SO₂] = 0.10 M and [O₂] = 0.040 M. A second, freshly charged converter at the same temperature reads [SO₃] = 0.10 M, [SO₂] = 0.20 M and [O₂] = 0.25 M. No calculator: take RT = 25 L·atm/mol, RT = 2500 J/mol, and ln 10 = 2.3. Work each line — every answer feeds the next. Determine whether this equilibrium favours products, working line by line from the concentrations.
38. The Position of Equilibrium — Bonus mark, worked backwards. A second contact-process converter at 300 K is reported only through its thermodynamics: ΔG° = −11.5 kJ/mol for 2SO₂(g) + O₂(g) ⇌ 2SO₃(g). Still no calculator: RT = 2500 J/mol, RT = 25 L·atm/mol, and ln 10 = 2.3. Determine the pressure equilibrium constant for this converter.
Acids & Bases
39. The pH scale — A standardised buffer in the stockroom is labelled: hydrogen-ion concentration 1 × 10⁻³ mol/L. Calculate the pH of the sample.
40. The pH scale — A rainwater sample caught off the science-wing roof measures 8.0 × 10⁻⁵ mol/L in hydrogen ion. Determine the pH of the sample, to two decimal places.
41. The Kw family — A weak monoprotic acid used in a titration practical has an acid dissociation constant of Ka = 1.0 × 10⁻⁹ at 25 °C. Calculate the acid's pKa.
42. The Kw family — A weak acid HA has Ka = 8.0 × 10⁻⁹ at 25 °C, where the ion product of water is Kw = 1.0 × 10⁻¹⁴. Its conjugate base A⁻ is the species left behind once the proton has gone. Determine Kb for the conjugate base A⁻ — the hypochlorite-style partner of this acid.
43. Weak acids and ICE — A weak monoprotic acid HA, Ka = 2.0 × 10⁻⁶, is made up to a formal concentration of 0.020 mol/L at 25 °C. Less than 5 % of it ionizes, so the x-is-small approximation applies. Calculate the pH of the solution.
44. Weak acids and ICE — The same weak acid HA (Ka = 8.0 × 10⁻⁶) sits at a formal concentration of 0.020 mol/L. A pH meter puts the equilibrium hydrogen-ion concentration at 4.0 × 10⁻⁴ mol/L. Calculate the percent ionization of the acid.
45. Buffer country — A buffer holding 1.00 mol/L of a conjugate base A⁻ and 0.200 mol/L of its weak acid HA reads pH 7.90 on a calibrated meter at 25 °C. Determine the pKa of the weak acid.
46. Buffer country — A buffer is made from hydrazine (pKb 5.89) and its conjugate acid, supplied as hydrazinium chloride. The flask holds 1.60 mol/L of the conjugate acid BH⁺ and 0.200 mol/L of the free base B, at 25 °C. Determine the buffer's pOH, and then its pH.
47. Dilution discipline — A protocol calls for 0.200 mol of solute to be delivered from a 0.400 mol/L stock solution. Determine the volume of stock the protocol requires.
48. Dilution discipline — A technician pipettes 40.0 mL of 1.50 mol/L stock into a volumetric flask and makes the contents up to a final volume of 200.0 mL with distilled water. Calculate the concentration of the diluted solution.
49. The burette — A 50.0 mL aliquot of hydrochloric acid of unknown concentration is pipetted into a conical flask with two drops of indicator. From the burette, 0.100 mol/L sodium hydroxide brings the flask to a lasting colour change after 30.0 mL. Acid and base react one-to-one, so n = 1. Determine the concentration of the acid.
50. The burette — The same titration, marked the long way: a 25.0 mL aliquot of a monoprotic acid takes 30.0 mL of 0.100 mol/L sodium hydroxide to reach the endpoint, one-to-one. This time the examiner wants the moles shown. Determine the amount of base delivered, then the acid's concentration.
51. The Titration Final — The last station of the practical exam. A 1.00 mol/L stock of sodium hydroxide is too strong to titrate with, so 10.0 mL of it is pipetted into a volumetric flask and made up to 500.0 mL. That diluted base then titrates a 50.0 mL aliquot of hydrochloric acid — strong, fully dissociated, one-to-one — and the endpoint lands at exactly 25.0 mL. Every number is chosen to work in your head, and every answer feeds the next line. Determine the acid's concentration, its pH, and its pOH — one line at a time.
52. The Titration Final — Bonus mark, and a decision to sign off on. The rinse water left in the flask is a weak monoprotic acid, formal concentration 0.010 mol/L, Ka = 1.0 × 10⁻⁶, ionizing well under 5 %. The building's discharge permit sets a floor of pH 2.50: anything more acidic than that must go to the neutralizing tank instead of the drain. Determine the rinse water's pH, then rule on where it goes.
Electrochemistry
53. Reading the table — A voltaic cell pairs a lead half-cell, Pb²⁺(aq) + 2e⁻ → Pb(s) at −0.13 V, with a second half-cell whose metal has rubbed off the label. The lead electrode is the cathode, and at standard conditions the cell delivers 0.32 V. Determine the standard reduction potential of the anode half-cell.
54. Reading the table — A voltaic cell pairs a lead half-cell, Pb²⁺(aq) + 2e⁻ → Pb(s) at −0.13 V, with a second half-cell whose metal has rubbed off the label. The lead electrode is the cathode, and at standard conditions the cell delivers 0.13 V. Determine the standard reduction potential of the anode half-cell.
55. Nernst, off standard — A nickel–silver cell operates at 25 °C. Its balanced cell reaction is Ni(s) + 2Ag⁺(aq) → Ni²⁺(aq) + 2Ag(s), and at standard conditions it delivers 1.06 V. In the working cell the Ni²⁺ solution is 0.0010 mol/L and the Ag⁺ solution is 1.0 mol/L. Calculate the cell potential under these conditions.
56. Nernst, off standard — A zinc–copper cell operates at 25 °C. Its balanced cell reaction is Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s), and at standard conditions it delivers 1.10 V. In the working cell the Zn²⁺ solution is 0.10 mol/L and the Cu²⁺ solution is 1.0 mol/L. Calculate the cell potential under these conditions.
57. Charge on the clock — An electrolytic cell in a school lab draws a steady 9.0 A for 10 min. Calculate the charge that passes through the cell.
58. Charge on the clock — An industrial rectifier holds 8.0 A through a cell for 2.0 h without interruption. Determine the total charge passed.
59. Faraday's scales — An electrolytic cell plates aluminum from a bath of Al³⁺ ions onto a steel blank. A coulometer records 57900 C through the cell. The molar mass of aluminum is 27.0 g/mol, and F = 96 500 C/mol. Calculate the mass of aluminum deposited.
60. Faraday's scales — An electrolytic cell plates zinc from a bath of Zn²⁺ ions onto a steel blank. A coulometer records 19300 C through the cell. The molar mass of zinc is 65.4 g/mol, and F = 96 500 C/mol. Calculate the mass of zinc deposited.
61. Time to plate — A work order calls for 38.1 g of copper on a batch of parts, and the line has a 100 min window to do it in. The bath carries Cu²⁺ ions, copper has a molar mass of 63.5 g/mol, and F = 96 500 C/mol. Determine the current the rectifier must hold.
62. Time to plate — A plating line runs a rack of parts through a copper bath at a steady 9.65 A for 50 min. The bath carries Cu²⁺ ions, copper has a molar mass of 63.5 g/mol, and F = 96 500 C/mol. Calculate the mass of copper deposited on the rack.
63. The Electroplating Shift — Last rack of the shift. A nickel plating cell runs from a bath of Ni²⁺ ions with inert anodes, where water is oxidized. The data sheet gives Ni²⁺(aq) + 2e⁻ → Ni(s) at −0.26 V and O₂(g) + 4H⁺(aq) + 4e⁻ → 2H₂O(l) at +1.23 V. The rectifier holds 19.3 A for 50 min, nickel has a molar mass of 58.7 g/mol, and F = 96 500 C/mol. The work order will not ship unless the rack carries at least 14.1 g. Work each line — every answer feeds the next. Determine whether this shift meets the work order, one line at a time.
64. The Electroplating Shift — Bonus mark, worked backwards. A test coupon comes off the same line 17.67 g heavier after 57900 C passed through an unlabelled cobalt bath. The molar mass of cobalt is 58.9 g/mol, and F = 96 500 C/mol. Determine how many electrons each ion in that bath took.
Gases & Solutions
65. Combined and ideal — A piston cylinder traps 10.0 L of an ideal gas at 120 kPa and 27 °C. The piston is driven in until the gas fills 5.0 L, and by then the gas has reached 77 °C. Calculate the pressure of the gas in its final state.
66. Combined and ideal — A fixed sample of an ideal gas starts at 150 kPa, 8.0 L and 27 °C. After a run through the plant it is found at 100 kPa in a 6.0 L receiver. Determine the sample's final absolute temperature, in kelvin.
67. Molar mass from the gas — An unlabelled cylinder in the prep room is vented into an evacuated bulb of known volume. The gas inside behaves ideally, and at 150 kPa and 77 °C a litre of it weighs 2.371 g. On this paper R = 8.314 kPa·L/(mol·K). Determine the gas's molar mass, then identify the gas.
68. Molar mass from the gas — An unlabelled cylinder in the prep room is vented into an evacuated bulb of known volume. The gas inside behaves ideally, and at 100 kPa and 47 °C a litre of it weighs 0.752 g. On this paper R = 8.314 kPa·L/(mol·K). Determine the gas's molar mass, then identify the gas.
69. Partial pressures — A rigid vessel holds 2.0 mol of oxygen and 3.0 mol of helium. The mixture reads 300 kPa on the vessel's gauge, and both gases behave ideally. Calculate the partial pressure of the oxygen.
70. Partial pressures — A gas header runs at a total pressure of 300 kPa and carries 6.0 mol of gas in all. A probe reports that the argon in the header exerts 225 kPa. Determine the amount of argon in the header.
71. Graham's race — Two identical vessels, one of He (4 g/mol) and one of CH₄ (16 g/mol), are held at the same temperature and pressure. Each is pierced with an identical pinhole and the gases are allowed to effuse. Determine how many times faster He effuses than CH₄.
72. Graham's race — Through one pinhole, CH₄ (16 g/mol) effuses at 48 mL/s. The same apparatus at the same temperature and pressure is then filled with SO₂ (64 g/mol). Calculate the effusion rate of the SO₂.
73. Three ways to say how much — A technician weighs 101 g of potassium nitrate (M = 101 g/mol), dissolves it, and makes the solution up to 250 mL in a volumetric flask. Calculate the molar concentration of the solution.
74. Three ways to say how much — A 0.5 mol sample of a non-volatile solute is stirred into 250 g of water. The solution is not made up to any particular volume — the water was simply weighed out first. Calculate the molality of the solution.
75. Colligative counting — A 0.5 mol/kg solution of a non-volatile, non-ionizing solute in water is cooled in a jacket. For water Kf = 1.86 °C·kg/mol, and pure water freezes at 0 °C. Determine the temperature at which this solution begins to freeze.
76. Colligative counting — A 1 mol/kg solution of a non-volatile, non-ionizing solute in water is heated on a hotplate at standard atmospheric pressure. For water Kb = 0.512 °C·kg/mol, and pure water boils at 100 °C. Determine the temperature at which this solution boils.
77. Vapour pressure stories — A solution is prepared from 3.0 mol of a non-volatile solute and 7.0 mol of a solvent whose pure vapour pressure at this temperature is 80 kPa. The mixture behaves ideally. Calculate the vapour pressure of the solvent above the solution.
78. Vapour pressure stories — Above an ideal solution whose solvent mole fraction is 0.6, a manometer reads a solvent vapour pressure of 36 kPa at the working temperature. Determine the vapour pressure of the pure solvent at that temperature.
79. The Gas Works — Last batch of the shift. The gas works draws 4.0 mol of carbon dioxide (44 g/mol) from the reservoir at STP — 101 kPa, 273 K, molar volume 22.4 L/mol. The compressor delivers it to the kiln line at 404 kPa and 819 K. Downstream the batch is blended into a header that carries 4 mol of nitrogen for every mole of the batch gas, and the header runs at 800 kPa in total. Work each line — every answer feeds the next. Determine, line by line, what the batch does on its way through the works.
80. The Gas Works — Bonus mark, and still no calculator. An unmarked cylinder is found behind the compressor house. Vented into a bulb at STP, its gas weighs 0.714 g per litre. At STP one mole of any ideal gas fills 22.4 L. Determine the gas's molar mass, and name the gas.