1) Methylamine, CH3NH2, is a weak base that ionizes in solution as shown by the following equation.
CH3NH2 + H2O <===> CH3NH3+ + OH¯
(a) At 25 °C, the percentage ionization in a 0.160-molar solution of CH3NH2 is 4.7%. Calculate [OH¯], [CH3NH3+], [CH3NH2], [H3O+], and the pH of a 0.160-molar solution of CH3NH2 at 25 °C.
(b) Calculate the value for Kb, the ionization constant for CH3NH2, at 25 °C.
(c) If 0.050 mole of crystalline lanthanum nitrate is added to 1.00 liter of a solution containing 0.20 mole of CH3NH2 and 0.20 mole of its salt CH3NH3Cl at 25 °C, and the solution is stirred until equilibrium is attained, will any La(OH)3 precipitate? Show the calculations that prove your answer. (The solubility product constant for La(OH)3, Ksp, is 1 x 10¯19 at 25 °C.
2) M(s) + Cu2+(aq) ---> M2+(aq) + Cu(s)
For the reaction above, E° = 0.740 volt at 25 °C.
(a) Determine the standard electrode potential for the reaction half-reaction M2+(aq) + 2 e¯ ---> M(s).
(b) A cell is constructed in which the reaction above occurs. All substances are initially in their standard states, and equal volumes of the solutions are used. The cell is then discharged. Calculate the value of the cell potential, E, when [Cu2+] has dropped to 0.20 molar.
(c) Find the ratio [M2+]aq / [Cu2+]aq when the cell reaction above reaches equilibrium.
(a) A solution containing 3.23 grams of an unknown compound dissolved in 100.0 grams of water freezes at -0.97 °C. The solution does not conduct electricity. Calculate the molecular weight of the compound. (The molal freezing point depression constant for H2O is 1.86 °C kg mole¯1.)
(b) Elemental analysis of this unknown compound yields the following percentages by weight: H = 9.74%; C = 38.70%; O = 51.56%. Determine the molecular formula of the compound.
(c) Complete combustion of a 1.05-gram sample of the compound with the stoichiometric amount of oxygen gas produces a mixture of H2O(g) and CO2(g). What is the pressure of this gas when it is contained in a 3.00-liter flask at 127 °C?
4) Answer FIVE of the eight options in this part. (Answer to more than five options will not be scored.)
(a) Solutions of sodium fluoride and dilute hydrochloric acid are mixed.
(b) A saturated solution of barium hydroxide is mixed with a solution of iron(III) sulfate.
(c) A solution of ammonium sulfate is added to a potassium hydroxide solution.
(d) Carbon dioxide gas is bubbled through a concentrated solution of sodium hydroxide.
(e) Solid copper is added to a dilute nitric acid solution.
(f) Chlorine gas is bubbled into a cold solution of dilute sodium hydroxide.
(g) A solution of potassium permanganate is mixed with an alkaline solution of sodium sulfite.
(h) Methyl iodine is heated with a solution of sodium hydroxide.
5) The decomposition of compound X is an elementary process that proceeds as follows:
| kf | ||
| X(g) | <===> | A(g) + B(g) |
| kr |
DH° for the above reaction = +15 kilocalories
The forward reaction is slow at room temperature but becomes rapid when a catalyst is added.
(a) Draw a diagram of potential energy versus reaction coordinate for the uncatalyzed reaction. On this diagram label
(1) the axes
(2) the energies of the reactants and the products
(3) the energy of the activated complex
(4) all significant energy differences
(b) On the same diagram indicate the change or changes that result from the addition of the catalyst. Explain the role of the catalyst in changing the rate of the reaction.
(c) If the temperature is increased, will the ratio kf / kr increase, remain the same, or decrease? Justify your answer with a one- or two-sentence explanation. (kf and kr are the specific rate constants for the forward and the reverse reactions, respectively.)
6) NH4Cl(s)------->NH3(g) +
HCl(g)
for this reaction, DH = +42.1 kilocalories
Suppose the substances in the reaction above are at equilibrium at 600 K in volume V and at pressure P. State whether the partial pressure of NH3(g) will have increased, decreased, or remained the same when equilibrium is reestablished after each of the following disturbances of the original system. Some solid NH4Cl remains in the flask at all times. Justify each answer with a one- or two-sentence explanation.
(a) A small quantity of NH4Cl is added.
(b) The temperature of the system is increased.
(c) the volume of the system is increased.
(d) A quantity of gaseous HCl is added.
(e) A quantity of gaseous NH3 is added.
(a) State the physical significance of entropy.
(b) From each of the following pairs of substances, choose the one expected to have the greater absolute entropy. Explain your choice in each case. Assume 1 mole of each substance.
(1) Pb(s) or C(graphite) at the same temperature and pressure
(2) He(g) at 1 atmosphere or He(g) at 0.05 atmosphere, both at the same temperature
(3) H2O(l) or CH3CH2OH(l) at the same temperature and pressure
(4) Mg(s) at 0 °C or Mg(s) at 150 °C, both at the same pressure.
8) Account for the difference in solubility described in each of the following experimental observations:
(a) BaCO3, BaSO3, and BaSO4 are only slightly soluble in water, but the first two dissolve in HCl solution whereas BaSO4 does not.
(b) CuS cannot be dissolved by warm, dilute HCl but it does dissolve in warm, dilute HNO3
(c) AgCl, Hg2Cl2, and PbCl2 are only slightly soluble in water, but AgCl does dissolve in ammonia solution whereas the other two do not.
(d) Fe(OH)3 and Al(OH)3 are only slightly soluble in water, but Al(OH)3 dissolves in concentrated NaOH whereas Fe(OH)3 does not.
(a) Write the ground-state electron configuration for an arsenic atom, showing the number of electrons in each subshell.
(b) Give one permissible set of four quantum numbers for each of the outermost electrons in a single As atom when it is in its ground state.
(c) Is an isolated arsenic atom in the ground state paramagnetic or diamagnetic? Explain briefly.
(d) Explain how the electron configuration of the arsenic atom in the ground state is consistent with the existence of the following known compounds: Na3As, AsCl3, and AsF5.
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