CHM2046 Discussion Class Worksheet 8 (Fall 2017)

Student Name___________________________________________________ Section #__________

1. To what do the "system", "surroundings", and "universe" refer?

"System" is the defined reaction or process in which you are interested; "surroundings" are the defined
things other than the system that are relevant to the reaction or process (e.g., an aqueous reaction taking
place in an insulated dewar or beaker is the system, whereas the water and the dewar/beaker are the
surroundings); and the "universe" is the defined system plus the defined surroundings.

2. What does it mean when it is said that a system is "spontaneous" under certain conditions?
A system undergos a "spontaneous" change when that change occurs by itself under specified conditions,
without continuous input of energy from outside the system (i.e., from the surroundings). For example,
once you crank the engine on your car, the combustion of fuel begins and continues spontaneously without
your having to continually and repeatedly crank the engine. Likewise, once your start to roll a ball down a
hill, it spontaneously rolls down the hill on its own without your having to continue to push it down the hill.
A "nonspontaneous" system will be a system for which continuous input of energy from the surroundings is
required.
Also, and this is very important, a reaction will proceed spontaneously to equilibrium, regardless of whether
the reaction is reactant- or product-favored, and any time something happens so that Q K, the reaction will
spontaneously shift toward the right or left to re-establish equilibrium so that Q = K.

3. Can the spontaneity (or lack thereof) of a system be ascertained by the H of the system alone?
No because some systems proceed spontaneously under specified conditions, regardless of H. For
example, both of the following chemical processes occur spontaneously at 25C:
H2O(g) H2O(l) H < 0 (exothermic)
CO2(s) CO2(g) H > 0 (endothermic)
Therefore, other thermodynamic variables must be known before spontaneity of a system can be
ascertained.

4. What is "entropy" ? Is entropy a state function like enthalpy ?

The degree of randomness or disorder in a system. Yes entropy is a state function like enthalpy.

5. What is the 2nd law of thermodynamics ?

The entropy change Suniverse must be > 0 for a spontaneous process, which means that (Ssystem + Ssurroundings)
must be > 0 for a spontaneous process. So, even if Ssystem is negative, you can still have a spontaneous
reaction if Ssurroundings is more positive, so that Suniverse = (Ssystem + Ssurroundings) > 0.
At equilibrium Suniverse = (Ssystem + Ssurroundings) = 0.

6. What is the 3rd law of thermodynamics ?

A perfect defect-free crystalline substance exhibits zero entropy at absolute zero K.

7. Which of the following reactions would be predicted to be spontaneous at relatively high temperatures
but nonspontaneous at relatively low temperatures ? Be sure to explain why in the space below the answer
options.
(1) an exothermic reaction with Sreaction < 0 (2) an exothermic reaction with Sreaction > 0
(3) an endothermic reaction with Sreaction < 0 (4) an endothermic reaction with Sreaction > 0
(5) a reaction with both Ssystem < 0 and Ssurroundings < 0
An endothermic reaction (Hreaction > 0) requires that the TSreaction component be sufficiently > 0 and large
enough in order to render the reaction spontaneous (Greaction < 0). Therefore Sreaction must be > 0 and T
must be relatively high.

8. If someone left the valve to a hydrogen gas tank open in a lab so that the partial pressures of H2 and N2
(in the air) in the lab reached 0.50 atm and 0.50 atm, respectively, would the following reaction forming
highly toxic liquid hydrazine (N2H4) become a concern (i.e., is the following reaction likely to occur at 25C,
given these partial pressures of H2 and N2) ? 2H2(g) + N2(g) N2H4(l) Greaction = 149 kJ/mol
(1) no concern because Qp > Kp and so G > 0 (2) yes concern because Qp > Kp and so G < 0
(3) yes concern because Qp < Kp and so G < 0 (4) no concern because Qp < Kp and so G > 0
(5) no concern because a reaction is always nonspontaneous when Sreaction < 0
(answer continued on next page)
Students need to calculate K from Greaction and then compare their calculated Q to their calculated K.
If Q > K (which it is), then G > 0 (which it is) and the reaction will favor reactants rather than products.

9. Select the false statement below.

(1) if G < 0, G represents the maximum free energy or useful work obtainable from the reaction system
(2) if G > 0, G represents the minimum work that must be done to the system for it to produce
product(s)
(3) if G = 0 then G can be either = 0 or > 0 or < 0 (Students will likely need help with this one.)
(4) G is based upon the difference between Keq and Q of a reaction system at some temperature T
(5) if G > 0 for a reaction at some temperature, that reaction is product-favored and Keq > 1 at that
temperature

10. Consider the following reactions with their respective thermochemical data and determine whether the
thermodynamic coupling of the reactions would result in the spontaneous (product-favored) reduction of
Fe2O3 to Fe metal at 298K and/or at 1000K. (Assume that Srxn and Hrxn do not change appreciably with
temperature.)
2Fe2O3(s) 4Fe(s) + 3O2(g)H = +1651 kJ/mol S = +549 J/Kmol
+ 6H2(g) + 3O2(g) 6H2O(g) H = 1451 kJ/mol S = 266 J/Kmol
= 2Fe2O3(s) + 6H2(g) 4Fe(s) + 6H2O(g) (hint: what is the G of this target reaction?)
(1) nonspontaneous at both temperatures (2) spontaneous at 1000K but nonspontaneous at 298K
(3) spontaneous at 298K but nonspontaneous at 1000K (4) spontaneous at both temperatures
(5) based on the thermodynamics of the target reaction, it is nonspontaneous at all temperatures

11. Calculate the free energy (G) for the following reaction if pieces of pure cadmium wire and pure iron
wire were placed in a solution containing 1.0 M Fe2+ ions and 0.010 M Cd2+ ions at 25C.
Cd(s) + Fe2+(aq) Cd2+(aq) + Fe(s) G = +7.2 kJ/mol at 25C
(1) 2.1 kJ/mol (2) +2.1 kJ/mol (3) 4.2 kJ/mol (4) +4.2 kJ/mol (5) 8.4 kJ/mol
(This is meant to be a preview of what we'll be getting into with electrochemistry later.)
________________________________________________________________________________________
Consider the formation reaction for CCl4(g) below when answering questions 1214.
C(graphite) + 2Cl2(g) CCl4(g) Kp = 2.57 x 109 at 25C.

12. Which of the following statements is false regarding this reaction at equilibrium at 25C ?
(1) Gsystem < 0 (2) Ssystem < 0 (3) the reaction is endothermic
(4) Gsystem = 0 (5) Ssurroundings > 0

13. In a reaction flask at 553K, 1.00 atm of gaseous Cl2 was allowed to react with the C(graphite) until
equilibrium was reached with the gaseous CCl4 product. At this temperature of 553K, the %-yield of gaseous
CCl4 was determined to be 90%. Determine Gsystem at 553K. (hint: what was the actual yield at 553K ?)
(1) 48.3 kJ/mol (2) 17.5 kJ/mol (3) 53.7 kJ/mol (4) 96.0 kJ/mol (5) 5.50 kJ/mol

14. If the reaction reaches standard-state equilibrium at 403C, use this information along with the Kp
information given for the reaction at 25C to determine the standard molar enthalpy of formation (Hf) of
gaseous CCl4. (ln(K1/K2) = (Hrxn / R){(1/T2) (1/T1)})
(1) 48.3 kJ/mol (2) 17.5 kJ/mol (3) 53.7 kJ/mol (4) 96.0 kJ/mol (5) 5.50 kJ/mol
Students will have to know that standard-state equilibrium means that Greaction = 0 and therefore Kp = 1,
then use this Kp and the Kp above with their respective T values in Kelvin to solve for the Hrxn which is Hf
of gaseous CCl4. Of course, R = 8.314 J/molK and Hrxn has to be in Joules/mol.