1) The acid ionization constant, Ka, for propanoic acid, C2H5COOH, is 1.3 x 10¯5.
(a) Calculate the hydrogen ion concentration, [H+], in a 0.20-molar solution of propanoic acid.
(b) Calculate the percentage of propanoic acid molecules that are ionized in the solution in (a).
(c) What is the ratio of the concentration of propanoate ion, C2H5COO¯, to that of propanoic acid in a buffer solution with a pH of 5.20 ?
(d) In a 100-milliliter sample of a different buffer solution, the propanoic acid concentration is 0.50-molar and the sodium propanoate concentration is 0.50-molar. To this buffer solution, 0.0040 mole of solid NaOH is added. Calculate the pH of the resulting solution.
2) The molecular formula of a hydrocarbon is to be determined by analyzing its combustion products and investigating its colligative properties.
(a) The hydrocarbon burns completely, producing 7.2 grams of water and 7.2 liters of CO2 at standard conditions.
(b) Calculate the mass in grams of O2 required for the complete combustion of the sample of the hydrocarbon described in (a).
(c) The hydrocarbon dissolves readily in CHCl3. The freezing point of a solution prepared by mixing 100. grams of CHCl3 and 0.600 gram of the hydrocarbon is -64.0 °C. The molal freezing-point depression constant of CHCl3 is 4.68 °C / molal and its normal freezing point is -63.5 °C. Calculate the molecular weight of the hydrocarbon.
(d) What is the molecular formula of the hydrocarbon?
3) 2 ClO2(g) + F2(g) ---> 2 ClO2F(g)
The following results were obtained when the reaction represented above was studied at 25 °C.
(a) Write the rate law expression for the reaction above.
(b) Calculate the numerical value of the rate constant and specify the units.
(c) In experiment 2, what is the initial rate of decrease of [F2]?
(d) Which of the following reaction mechanisms is consistent with the rate law developed in (a)? Justify your choice.
I.
ClO2 + F2 <---> ClO2F2 (fast)
ClO2F2 ---> ClO2F + F (slow)
ClO2 + F ---> ClO2F (fast)
II.
F2 ---> 2 F (slow)
2 (ClO2 + F ---> ClO2F) (fast)
4) Give the formulas to show the reactants and the products for FIVE of the following chemical reactions. Each of the reactions occurs in aqueous solution unless otherwise indicated. Represent substances in solution as ions if the substance is extensively ionized. Omit formulas for any ions or molecules that are unchanged by the reaction. In all cases a reaction occurs. You need not balance.
Example: A strip of magnesium is added to a solution of silver nitrate.
Mg + Ag+ ---> Mg2+ + Ag
(a) Solid aluminum oxide is added to a solution of sodium hydroxide.
(b) Solid calcium oxide is heated in the presence of sulfur trioxide gas.
(c) Equal volumes of 0.1-molar sulfuric acid and 0.1-molar potassium hydroxide are mixed.
(d) Calcium metal is heated strongly in nitrogen gas.
(e) Solid copper(II) sulfide is heated strongly in oxygen gas.
(f) A concentrated solution of hydrochloric acid is added to powdered manganese dioxide and gently heated.
(g) A concentrated solution of ammonia is added to a solution of zinc iodide.
(h) A solution of copper(II) sulfate is added to a solution of barium hydroxide.
5) BCl3(g) + NH3(g) <---> Cl3BNH3(s)
The reaction represented above is a reversible reaction.
(a) Predict the sign of the entropy change, DS, as the reaction proceeds to the right. Explain your prediction.
(b) If the reaction spontaneously proceeds to the right, predict the sign of the enthalpy change, DH. Explain your prediction.
(c) The direction in which the reaction spontaneously proceeds changes as the temperature is increased above a specific temperature. Explain.
(d) What is the value of the equilibrium constant at the temperature referred to in (c); that is, the specific temperature at which the direction of the spontaneous reaction changes? Explain.
An experiment is to be performed to determine the molecular mass of a volatile liquid by the vapor density method. The equipment shown above is to be used for the experiment. A barometer is also available.
(a) What data are needed to calculate the molecular mass of the liquid?
(b) What procedures are needed to obtain these data?
(c) List the calculations necessary to determine the molecular mass.
(d) If the volatile liquid contains nonvolatile impurities, how would the calculated value of the molecular mass be affected? Explain your reasoning.
7) Explain each of the following.
(a) When an aqueous solution of NaCl is electrolyzed, Cl2(g) is produced at the anode, but no Na(s) is produced at the cathode.
(b) The mass of Fe(s) produced when 1 faraday is used to reduce a solution of FeSO4 is 1.5 times the mass of Fe(s) produced when 1 faraday is used to reduce a solution of FeCl3.
Zn + Pb2+ (1-molar) ---> Zn2+ (1-molar) + Pb
(c) The cell that utilized the reaction above has a higher potential when [Zn2+] is decreased and [Pb2+] held constant, but a lower potential when [Pb2+] is decreased and [Zn2+] is held constant.
(d) The cell that utilizes the reaction given in (c) has the same cell potential as another cell in which [Zn2+] and [Pb2+] are each 0.1-molar.
8) Experimental data provide the basis for interpreting differences in properties of substances.
Account for the differences in properties given in Tables 1 and 2 above in terms of the differences in structure and bonding in each of the following pairs.
(a) MgCl2 and SiCl4
(b) MgCl2 and MgF2
(c) F2 and Br2
(d) F2 and N2
9) Explain each of the following in terms of nuclear models.
(a) The mass of an atom of 4He is less than the sum of the masses of 2 protons, 2 neutrons, and 2 electrons.
(b) Alpha radiation penetrates a much shorter distance into a piece of material than does beta radiation of the same energy.
(c) Products from a nuclear fission of a uranium atom such as 90Sr and 137Ce are highly radioactive and decay by emission of beta particles.
(d) Nuclear fusion requires large amounts of energy to get started, whereas nuclear fission can occur spontaneously, although both processes release energy.
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