CHEM 1001 S QUIZ # 3 August 14, 2009 DATA 75 min

NAME ______________________________ St # ___________________________

F = 96,485 C mol-1 R = 8.3144 J K-1 mol-1 at 298K RT/nF ln Q = 0.0592/n log Q ln X = 2.303 log X

2.303RT = 5.7 kJ/mol at 298 K Coulomb volt = Joule

amp = coulomb/sec

1.[10 mk] a) Predict the signs of G, H and S for the following at 298 K and 1 atm. i) C3H8 (g) + 5 O2 (g) 4 H2O (l) (burning propane) ii) I2 (s) I2 (g) (subliming iodine) + 3 CO2 (g) Go __________ Ho _______ So _________ Go __________ Ho _______ So _________

iii)

For I2 (s) Tables give Gof = 0 and Hof = 0 kJ mol-1and So = 260.7 Jmol-1K-1 at 298 K . Explain why Go does not equal Ho - T So

b) Give the oxidation number for N in Cr in KNO2 ________ K2Cr2O7 _______ HNO3 _________ in NH4+ _________ CrO42- _______

Cr(NO3)3 __________

c) Give the balanced chemical reaction whose Hof corresponds BY DEFINITION to the standard enthalpy of formation of cupric carbonate, CuCO3 (s) at 298 K..

2. [10 mk] Complete and balance ANY TWO of the following reactions. Enter the coefficients and any added H+ , OH- or H2O directly on the line with the reaction for easy marking. (Any work may be done below the line). DO ONLY TWO OF A, B and C. A) in ACID PbO2 (s) + HOBr Pb2+ + BrO4_________________________________________________________________

Identify the oxidizing agent a) _____________ B) in BASE N2H4 + Fe(CN)63- N2 + Fe(CN)64_________________________________________________________________

Identify the reducing agent in b) _____________ C) in BASE Cl2 (g) OCl+ Cl_______________________________________________________ DO C ONLY IF YOU SKIPPED A or B

What type of redox reaction is c?

__________________

3.[12] Use the following reduction potential diagram to answer the questions below at standard conditions. +0.56 V MnO4
-

MnO4

2-

+2.26 V +1.0 V +1.5 V -1.20 V +3 2+ MnO2 (s) Mn Mn Mn (s) +1.23 V O2 H2O ________

0.0 V H+ H2

a) Give one Mn species which will reduce water ( H+) to H2 in 1 M H+ b) Give one Mn species listed which will oxidize water to O2 . c) Give one Mn species which disproportionates

__________

______________

d) Which couple above will be pH independent? ____________________________ e) Obtain the skip-step half cell potential for MnO4+ 3 e- MnO2 (s). Eo =
______________________

f) The biochemical standard state for H+ is pH = 7. Give a balanced half reaction for the O2 H2O reduction. Then use the Nernst equation to obtain the reduction potential for O2 at pH = 7 and 1 atm O2. O2 H2O _________________________________________________________

4. [13] Refer to thermodynamic data in the Table at 298.15 K Hof kJ/mol Gof kJ/mol So J K-1mol-1 Br (g) 111.9 82.42 174.9 Br (aq) -121.6 -104.0 82.4 Br2 (g) 30.91 3.14 245.4 Br2 (l) 0 0 152.2 BrCl (g) 14.64 -0.98 240 .0 BrCl (l) _____ -0.90 ____

RT ln(X) = 5.7 log(X) at 298 K R = 8.3144 J K-1 mol-1

a) Obtain the vapor pressure above liquid Br2 at 298 K _____________its heat of vaporization. _____________ and an approximate boiling point in degrees C ____________.

b) Obtain the Br-Br bond energy in Br2 ______________.

c) Is BrCl a liquid or a gas at 298 K and 1 atm pressure ? ________ d) Obtain the equilibrium constant for the reaction Br2 (l) + Cl2 (g) D 2 BrCl (g) at 298 K ______________

e) Obtain G for the reaction in c at the non-standard pressures of 1.41 atm for BrCl and 0.10 atm for Cl2 . G = ______________ Will the reaction proceed to the right, left, or neither? __________

5. [10mk] An electrochemical cell consists of two half cells, one a silver wire dipped into 10 ml of 0.20 M solution of Ag+ and the other a nickel bar dipped into 10 ml of a 0.4 M Ni2+ solution. They are connected via a KNO3 salt bridge.. Reduction potentials Ag+/Ag Eo = + 0.79 V , Ni2+/Ni Eo = -0.25 V. a) Write the net spontaneous cell reaction and obtain Ecell under the specified conditions.. _____________

b) Which electrode is the cathode?

Circle one :

silver

or

nickel

c) If the cell operates at 10 amps, how long can it run until it goes dead. (HINT one component has dropped to zero concentration.)