OWL Tutorial 2A-Prep (Ch.5.5-end + Ch.

18 all)

Question 1:

You have a large balloon containing 1.0 mol of gaseous water vapor at 70 °C. How will the
following step affect the internal energy of the system?

A) The temperature of the system is raised to 100 °C.

- The internal energy will decrease.

- The internal energy will remain unchanged.
- The internal energy will increase.

B) The vapor is frozen to a solid, at –20 °C.

- The internal energy will decrease.

- The internal energy will remain unchanged.
- The internal energy will increase.
VISUALIZATION
Heat and Work I

Question 2:
When a system gains energy that energy can be used to do a number of things. It can increase the
temperature of the system, it can cause a phase change, or it can perform work. Watch the
animation here of two systems involving the sublimation of solid carbon dioxide and answer the
questions that follow. The upper animation shows a few of the molecules of carbon dioxide when
dry ice is sealed in a flexible plastic bag. The lower animation shows carbon dioxide molecules
sealed in a rigid, stoppered container. In both animations the temperature of the carbon dioxide
increases.

1. Watch the animation of sublimation of CO2 in the sealed flask. Is there any movement of
the flask or any object outside the flask?

- Yes
- No

2. Is any work done during the sublimation of CO2 in the sealed flask?

- Yes
- No

3. What is the relationship between the quantity of energy transferred into the flask, Ein, and
the change in energy of the contents of the flask, ΔE?

- ΔE = Ein
- ΔE > Ein
- ΔE < Ein

4. Now examine the CO2 expanding in the plastic bag. Is any work done by this system?

- Yes
- No

5. For the plastic bag, what is the relationship between the quantity of energy transferred
into the bag, Ein, and the change in energy of the contents of the bag, ΔE?

- ΔE = Ein
- ΔE > Ein
 - ΔE < Ein

Question 3:

You wish to know the enthalpy change for the formation of liquid PCl3 from the elements.

P4 (s) + 6 Cl2 (g) 4 PCl3 (l) f H° =?

The enthalpy change for the formation of PCl5 from the elements can be determined
experimentally, as can the enthalpy change for the reaction of PCl3 (l) with more chlorine to
give PCl5 (s):

P4 (s) + 10 Cl2 (g) 4 PCl5 (s) f H° = -1774.0 KJ/mol – rxn

PCl3 (l) + Cl2 (g) PCl5 (s) f H° = -123.8 KJ/mol – rxn

Use these data to calculate the enthalpy change for the formation of 2.70 mol of PCl3 (l) from
phosphorus and chlorine.
Question 4:
Methanol CH3OH (l) and ethanol C2H5OH (l) both react with O2 and can be used as fuels.

CH3OH (l) + 3/2 O2 (g) CO2 (g) + 2H2O (g)

C2H5OH (l) + 3 O2 (g) 2 CO2 (g) + 3 H2O (g)

Use thermodynamic data in the table below.

f H°
Compound
(KJ/mol)
CH3OH (l) –238.4
C2H5OH (l) –277.0
H2O (g) –241.83
CO2 (g) –393.509

A) Calculate the specific heat of the reaction methanol with oxygen.

B) Calculate specific heat of the reaction ethanol with oxygen.

C) Decide whether the reaction of methanol or ethanol with oxygen provides more energy
per gram.

- Methanol gives more heat per gram when reacting with oxygen.
- Ethanol gives more heat per gram when reacting with oxygen.
- The compounds give almost the same heat per gram when reacting with oxygen.
INTERACTIVE EXAMPLE
Constant Volume Calorimetry

Question 5:

Octane, C8H18, a primary constituent of gasoline, burns in air:

C8H18(ℓ) + 12 1/2 O2(g) → 8 CO2(g) + 9 H2O(ℓ)

A 1.00-g sample of octane is burned in a constant volume calorimeter. The calorimeter is in an

insulated container with 1.20 kg of water. The temperature of the water and the bomb rises from
25.00 °C (298.15 K) to 33.21 °C (306.36 K). The heat required to raise the bomb’s temperature
(its heat capacity), Cbomb, is 837 J/K. The specific heat of water is 4.184 J/g∙K. What is the heat
of combustion per gram of octane? What is the heat of combustion per mole of octane?
Question 6:

Insoluble Li2CO3 (s) precipitates when solutions of Na2CO3 (aq) and LiCl (aq) are mixed.

Na2CO3 (aq) + 2 LiCl (aq) Li2CO3 (s) + 2 NaCl (aq)

To measure the enthalpy change, 400. mL of 0.55 M Na2CO3 (aq) and 400. mL of 1.1 M LiCl
(aq) are mixed in a coffee-cup calorimeter. The temperature of the mixture rises by 1.1 °C.
Calculate the enthalpy change for the precipitation of Li2CO3 (s) in kJ/mol. (Assume the density
of the solution is 1.0 g/mL, and its specific heat capacity is 4.2 J/g · K.)
Question 7:

The meals-ready-to-eat (MREs) in the military can be heated on a flameless heater. You can
purchase a similar product called "Heater Meals." Just pour water into the heater unit, wait a few
minutes, and you have a hot meal. The source of energy in the heater is

Mg (s) + 2 H2O (l) Mg (OH)2 (s) + H2 (g)

Calculate the enthalpy change under standard conditions, in joules, for this reaction. What
quantity of magnesium is needed to supply the energy required to warm 35 mL of water (d =
1.00 g/mL) from 24 °C to 90. °C? The specific heat capacity of water is 4.184 J/g ⋅ °C.

Compound f H° (KJ/mol)
Mg (OH)2 (s) -924.54
H2O (l) -285.83

The "heater meal" uses the reaction of magnesium with water as a source of energy as heat.
VISUALIZATION
Entropy and Mixing

Question 8:

Entropy generally increases when a pure liquid or solid dissolves in a solvent. This module
explores the mixing of water and propanol, CH3CH2CH2OH. The mixing of these two liquids is
shown as a slide show on the macroscale and depicted as a nanoscale animation.

A) Examine the Macroscale visualization. Do the liquids H2O and CH3CH2CH2OH appear
miscible?

- Yes
- No

B) Examine both the macroscale video and nanoscale animation of the mixing process.
Consider the water molecules Consider the water molecules. Are the water molecules
spread out over a larger volume before or after mixing?

- Before
- After

C) Consider the propanol molecules. Are the propanol molecules spread out over a larger
volume before or after mixing?

- Before
- After
Entropy Change: Predict Sign, Calculate from Standard Entropy
Values

Question 9:

Consider the reaction 2CO(g) + 2NO(g) 2CO2(g) + N2(g)

Based upon the stoichiometry of the reaction, the sign of Sºrxn should be ______?

Using standard thermodynamic data, calculate Sºrxn at 25°C.

SIMULATION
The Second Law of Thermodynamics

Question 10:

The 2nd Law of Thermodynamics states that for a reaction to be spontaneous, it must result in an
overall increase in the entropy of the universe. The entropy change for the universe can be
calculated by adding the entropy change for the system, ∆S°system, and the entropy change of the
surroundings caused by the exchange of thermal energy between the system and the
surroundings,

∆S°universe = ∆Sºrxn + (-∆Hºrxn / T)

This simulation allows for the exploration of the entropy changes that occur for five different
reactions. The temperature can be adjusted and the values for the entropy change to the system,
surroundings, and the universe are reported.

1. Select the last reaction, which is the formation of NOCl from NO and Cl2. Set the
temperature to 400 K. What is the entropy change to the system, ∆S°system, at this
temperature, in J.K-1.mol-1?

2. Does the value for ∆S°system change as temperature is changed?

- Yes
- No
3. Now observe the value of entropy change to the surroundings. Does this value change as
temperature changes?

- Yes
- No

4. Examine all five reactions, paying attention to the value of ∆S°surroundings as temperature is
increased. In general, how does the magnitude (the absolute value) of
∆S°surroundings change as temperature increases?

- Always increases
- Always decreases
- No definite pattern

5. Which of the following is true?

- Exothermic reactions lead to positive values of ∆S°surroundings.

- Exothermic reactions lead to negative values of ∆S°surroundings.

6. Consider the formation of NOCl again. Is the reaction product-favored, according to the
2nd Law of Thermodynamics, if run at a temperature of 400K?

- Yes
- No

7. Is the same reaction favored at 700 K?

- Yes
- No

8. Consider the simple case of the vaporization of water, the third reaction listed.
Experience tells us that (at 1 atm) liquid water will boil at temperatures above 373 K but
water vapor will condense, the opposite reaction, at lower temperatures. What is the value
of ∆S°universe at 300 K, in units of J K-1 mol-1?

9. Is the vaporization of water favored to occur at 300 K, according to the 2nd Law of
Thermodynamics?

- Yes
- No
10. Now examine the reaction at 400 K. What is ∆S°universe?

11. Is the vaporization of water favored to occur at 400 K, according to the 2nd Law of
Thermodynamics?

12. Consider the origin of the value of ∆S°universe

∆S°universe = ∆Sºrxn + (-∆Hºrxn / T)

Which of the two terms, ∆S°rxn or ∆H°rxn, will be most responsible for controlling the
sign of ∆S°universe at low temperatures?

- ∆S°rxn
- ∆H°rxn

13. Consider the origin of the value of ∆S°universe

∆S°universe = ∆Sºrxn + (-∆Hºrxn / T)

Which of the two terms, ∆S°rxn or ∆H°rxn, will be most responsible for controlling the
sign of ∆S°universe at high temperatures?

- ∆S°rxn
- ∆H°rxn
Summary:

The 2nd Law of Thermodynamics states that for a reaction to be product-favored, it must result in

an overall increase in the entropy of the universe. The entropy change for the universe can be

calculated by considering the entropy change for the reacting system, ∆S°system, and the entropy

change of the surroundings caused by the exchange of thermal energy between the system and

the surroundings.

Both the enthalpy change and the entropy change of the system are nearly constant with changes

in temperature. Because the enthalpy term is divided by the temperature at which the reaction

occurs, the importance of the ∆S°surroundings term decreases with increasing temperature.

At sufficiently low temperatures, the sign of ∆H°rxn will control the sign of ∆S°universe and

determine whether or not the reaction is thermodynamically favored.

At sufficiently high temperatures, the sign of ∆S°rxn will control the sign of ∆S°universe and

determine whether or not the reaction is thermodynamically favored.

Question 11:

A) Calculate ∆S°system, ∆S°surroundings and ∆S°universe for the following process at 298 K:
HNO3(g) HNO3 (aq)

Compound f H° (KJ/mol) S° (J/mol. k)

HCl (g) –135.06 266.38
HCl (aq) –207.36 146.4

B) Calculate ∆S°system, ∆S°surroundings and ∆S°universe for the following process at 298 K:
KOH(s) KOH (aq)

S°
f H°
(J/mol.
(KJ/mol)
Compound k)
 KOH (s) –424.72 78.9
KOH (aq) –482.37 91.6

Question 12:
A cave in Mexico was recently discovered to have some interesting
chemistry. Hydrogen sulfide, H2S, reacts with oxygen in the cave to
give sulfuric acid, which drips from the ceiling in droplets with a pH
less than 1

The reaction occurring is: H2S (g) + 2 O2 (g) H2SO4 (l)

Thermodynamic data are given below:

Compound H2S (g) O2 (g) H2SO4 (l)

f H° (KJ/mol) -20.63 0 -814

S° (J/mol. k) 205.79 205.07 156.9

A) What are the values of r H°, r S°, and r G°?

B)