Chemistry 7th Edition McMurry

Solutions Manual
Visit to Download in Full:
https://testbankdeal.com/download/chemistry-7th-edition-mcmurry-solutions-manual/
 CHAPTER 9
THERMOCHEMISTRY: CHEMICAL ENERGY

Chapter Learning Goals for Students

Section 9.1 Calculate the kinetic energy of an object in motion.

Convert between common units for energy.

Differentiate between the concepts of heat and temperature.

Section 9.2 Identify state functions.

Identify the sign of heat and work.

Section 9.3 Calculate PV work.

Section 9.4 Calculate the internal energy change (∆E) for a reaction.

Section 9.5
and
Section 9.6 Given a thermochemical equation and the amount of reactant or product, calculate
the amount of heat transferred.

Classify endo- and exothermic reactions.

Section 9.7 Calculate heat capacities, temperature changes, or heat transfer, using the equation
for heat capacity (C), specific heat (c) or molar heat capacity (Cm).

Calculate enthalpy changes in a calorimetry experiment.

Section 9.8 Use Hess’s law to find ∆H for an overall reaction, given reaction steps and their ∆H
values.

Section 9.9 Identify standard states of elements.

Write standard enthalpy of formation reactions (∆H°f) for compounds from their
elements.

Use values of standard heats of formation (∆H°f) for elements and compounds to
calculate ∆H° for a reaction.

Section 9.10 Use bond dissociation energies to estimate ∆H° for a reaction.

Section 9.11 Calculate ∆Hc for various fuels using thermochemical principles such as Hess’s law,
calorimetry and/or bond dissociation enthalpies.

Section 9.12
and
Section 9.13 Predict the sign of the entropy change (∆S) given the chemical equation or a
molecular diagram.

70
 Chapter 9—Thermochemistry: Chemical Energy

Using the relationship between the Gibbs free energy (∆G) and spontaneity, predict
the sign of ∆G, ∆H, ∆S.

Use ∆H and ∆S to determine the temperature at which a reversible system is at

equilibrium.

71
 Chapter 9—Thermochemistry: Chemical Energy

Lecture Outline
9.1. Energy and Its Conservation1
A. Energy
1. Capacity to do work or supply heat
2. Energy = work + heat
B. Kinetic energy
1. Energy of motion
2. EK = 1/2mv2
C. Potential energy – stored energy
D. Joule
1. SI unit for energy
2. 1 J = 1(kg⋅m2)/s2
E. Calorie
1. Amount of energy necessary to raise the temperature of 1 g of water by 1°C
2. 1 cal = 4.184 J
F. Law of Conservation of Energy
1. Energy can be neither created nor destroyed
2. It can only be converted from one form into another
G. Many forms of energy
1. Thermal energy
a. Kinetic energy of molecular motion
b. Temperature – measure of the kinetic energy of molecular motion
2. Heat
a. Energy transferred from one object to another
b. Result of a temperature difference between them
3. Chemical energy
a. A type of potential energy
b. Chemical bonds of molecules act as the storage medium
H. First Law of Thermodynamics: The energy of the universe is constant.
9.2. Internal Energy and State Functions2
A. System – everything we focus on in an experiment
B. Surroundings – everything other than the system
C. Internal energy – energy of the system
D. System isolated from the surroundings
1. No energy transfer to surroundings
2. ∆E = 0
3. First Law of Thermodynamics: The total internal energy of an isolated system is constant.
E. System is not isolated from surroundings
1. Energy flows to or from surroundings
2. ∆E = Efinal – Einitial
F. Energy changes measured from the point of view of the system
1. Energy flows out of system to surroundings – negative value
2. Energy flows into system from surroundings – positive value
G. State function – function or property whose value depends only on the present state (condition)
of the system, not on path used to arrive at that condition
1. Reversible
2. Overall change is zero if system returns to its original condition
9.3. Expansion Work3

1
Test Item File Questions: Multiple Choice 1, Algorithmic 1 – 3, Short Answer 1 – 7
2
Test Item File Questions: Multiple Choice 2, Algorithmic 4 – 8, Short Answer 8 – 12
3
Test Item File Questions: Multiple Choice 3 – 6, Algorithmic 9
72
 Chapter 9—Thermochemistry: Chemical Energy

A. Work
1. Force (f) that produces movement of an object times distance moved (d)
2. w = F × d
B. Expansion work (PV work)
1. Work done as result of volume change in the system
2. w = – (P × ∆V)
3. Expansion of the system.
a. System does work on surroundings
b. ∆E is negative
c. w = – P∆V
i. Work is negative
ii. ∆V is positive
4. Contraction of the system
a. Surroundings do work on the system
b. ∆E is positive
c. w = – P∆V
i. Work is positive
ii. ∆V is negative
9.4. Energy and Enthalpy4
A. Total energy change of a system
1. ∆E = q + w (q = heat)
2. ∆E = q + (– P∆V)
B. Amount of heat transferred: q = ∆E + P∆V
C. Reactions carried out with constant volume
1. ∆V = 0
2. No PV work done
3. qv = ∆E
D. Reactions carried out at constant pressure
1. ∆V ≠ 0
2. Energy change due to both heat transfer and PV work
3. qp = ∆E + P∆V
E. Heat of reaction, ∆H
1. Enthalpy change of a system
2. ∆H = ∆E + P∆V
3. State function – value depends only on the current state of the system
4. ∆H = Hproducts – Hreactants
5. Amount of heat released in a specific reaction depends on actual amounts of reactants.
9.5. Thermodynamic Equations and the Thermodynamic Standard State5
A. Value of enthalpy change, ∆H, reported for a reaction represents amount of heat released when
reactants converted to products in molar amounts represented by coefficients of the balanced
equation.
1. Actual amount of heat involved in a reaction depends on actual amounts of reactants.
2. Physical states of reactants and products must be specified.
B. Temperature and pressure also must be reported. Thermodynamic Standard State = 298.15 K
(25°C), 1 atm pressure of each gas, 1 M concentration (for solutions)
1. Allows different reactions to be compared
2. Indicated by addition of a superscript o, ∆H°
C. Standard enthalpy of reaction – enthalpy change measured under standard conditions
1. ∆H° values for a given equation
a. Equation balanced for number of moles of reactants and products

4
Test Item File Questions: Multiple Choice 7 – 15, Algorithmic 10 – 12, Short Answer 13 – 17
5
Test Item File Questions: Multiple Choice 16 – 21, Algorithmic 13 – 15
73
 Chapter 9—Thermochemistry: Chemical Energy

b. All substances are in standard states

c. Physical state of each substance specified
d. Refers to reaction going in direction written
e. Reversing direction of reaction changes sign of ∆H°
9.6. Enthalpies of Physical and Chemical Changes6
A. Enthalpies of chemical change
1. Heats of reaction – enthalpies of chemical change
2. Endothermic reactions
a. Hproducts > Hreactants
b. Heat flows into system from surroundings
c. ∆H is positive
3. Exothermic reactions
a. Hproducts < Hreactants
b. Heat flows to surroundings from system
c. ∆H is negative
B. Enthalpies of physical change
1. Heat of fusion – amount of heat required for melting
2. Heat of vaporization – amount of heat required for evaporation
3. Sublimation
a. Direct conversion of solid to vapor without going through a liquid state
b. Heat of sublimation = Heat of fusion + Heat of vaporization
9.7. Calorimetry and Heat Capacity7
A. Calorimetry – experimental technique that allows energy change associated with a chemical or
physical process to be determined
1. Temperature change observed when system gains or loses energy in the form of heat
2. Performed in a calorimeter
3. For an exothermic reaction: amount of heat released by reaction = amount of heat gained by
calorimeter + amount of heat gained by solution
B. Heat capacity (C)
q
C=
DT
1. Amount of heat required to raise the temperature of an object or substance a given amount
2. Extensive property
C. Specific heat
1. Amount of heat necessary to raise the temperature of exactly 1 g of a substance by exactly
1°C
2. q = (specific heat) × (mass of substance) × (∆T)
D. Molar heat capacity (Cm)
1. Amount of heat necessary to raise the temperature of 1 mole of a substance by 1°C
2. qm = (Cm) × (moles of substance) × (∆T)
9.8. Hess’s Law8
A. Hess’s law
1. Overall enthalpy change for a reaction is equal to the sum of the enthalpy changes for
individual steps in the reaction
2. Reactants and products in the individual steps added and subtracted like algebraic
quantities in determining the overall equation
B. Combine individual reactions so that their sums will be the desired reaction – textbook example
9.7

6
Test Item File Questions: Multiple Choice 22 – 33, Algorithmic 16 – 23,
7
Test Item File Questions: Multiple Choice 34 – 41, Algorithmic 24 – 31, Short Answer 18 – 20
8
Test Item File Questions: Multiple Choice 42 – 44, Algorithmic 32 – 34, Short Answer 21
74
 Chapter 9—Thermochemistry: Chemical Energy

9.9. Standard Heats of Formation9

A. Standard heat of formation
1. Enthalpy change ∆Hof for the hypothetical formation of 1 mole of a substance in its standard
state from the most stable forms of its constituent elements in their standard states
2. The most stable forms of all elements in their standard state have ∆Hof = 0.
B. Standard enthalpy change found by subtracting the sum of the heats of formation of reactants
from the sum of the heats of formation of products:
DH o = S DH products
o
- S DH reactants
o

C. Textbook Appendix B
9.10. Bond Dissociation Enthalpies10
A. Bond dissociation enthalpies
1. Enthalpy changes, ∆H°, for corresponding bond-breaking reactions
2. ∆H° = D = bond dissociation energy
3. Always positive
4. Always need energy to break a bond
B. ∆H° = D(bonds broken) – D(bonds formed)
C. Textbook Table 7.2
9.11. Fossil Fuels, Fuel Efficiency, and Heats of Combustion11
A. Heat of combustion (∆Hoc) – amount of energy released on burning a substance
B. Fuel efficiency
1. Calculate ∆Hoc in kJ/g or kJ/mL
2. Can compare efficiency for different fuels
C. Fossil fuels
1. Decayed remains of organisms from previous geological eras
2. Coal, natural gas and petroleum
a. Coal and petroleum – complex mixture of compounds
b. Coal – vegetable origin, compounds structurally similar to graphite
c. Petroleum – viscous liquid mixture of hydrocarbons, primarily marine origin
9.12. An Introduction to Entropy12
A. Spontaneous process
1. Process that proceeds on its own without continuous external influence
2. Need either a release of energy or an increase in disorder of the system
B. Entropy (S)
1. Amount of molecular disorder or randomness in a system
2. Larger the value of S, greater the molecular randomness
3. ∆S = Sfinal – Sinitial
4. Sfinal > Sinitial
a. ∆S is positive
b. System has become more random
5. Sfinal < Sinitial
a. ∆S is negative
b. System has become less random
C. Spontaneous process
1. Favored by decrease in H (negative ∆H)
2. Favored by increase in S (positive ∆S)

9
Test Item File Questions: Multiple Choice 45 – 49, Algorithmic 35 – 37
10
Test Item File Questions: Multiple Choice 50 – 53, Algorithmic 38 – 39
11
Test Item File Questions: Multiple Choice 54 – 56
12
Test Item File Questions: Multiple Choice 57 – 64, Algorithmic 40 – 43, Short Answer 22
75
 Chapter 9—Thermochemistry: Chemical Energy

9.13. An Introduction to Free Energy13

A. Gibbs free-energy change (∆G); ∆G = ∆H – T∆S.
B. Sign of ∆G used as a criterion for determining spontaneity of a process
1. ∆G negative – spontaneous
2. ∆G positive ≠ nonspontaneous
C. Temperature dependence (T∆S) term for ∆G.
1. Spontaneity of some processes depends on temperature
2. Low temperatures – ∆H dominates and controls spontaneity
3. High temperatures – T∆S dominates and controls spontaneity
D. ∆G = 0
1. Process at equilibrium
2. Balanced between spontaneous and nonspontaneous
3. Temperature at which a nonspontaneous reaction becomes spontaneous
DH
T=
DS

Inquiry – How is the Energy Content of New Fuels Determined?

13
Test Item File Questions: Multiple Choice 65 – 75, Algorithmic 44 – 47, Short Answer 23 – 25
76
 Chapter 9—Thermochemistry: Chemical Energy

CHAPTER 9
THERMOCHEMISTRY: CHEMICAL ENERGY

Teaching Tips, Points of Emphasis, and Common Misconceptions

Section 9.2 Students need to relate direction of heat flow with observed temperature change.
Demonstrate that for a chemical reaction (system) performed in a beaker
(surroundings), if heat energy is released by the system, the beaker absorbs the heat
and becomes hotter; if heat energy is absorbed by the system, the beaker contributes
the heat and becomes colder.

Section 9.2 It is important for students to understand that the amount of energy released or gained
in a reaction is proportional to the amounts of reactants and products involved in the
reaction.

Section 9.3 Gases do work when the molecules push against the walls of their container and the
volume of the container increases. If there is no volume change, no work is done.

Section 9.4 Relate energy change to physical work: When a person does work, the person’s
energy diminishes, so when a system does work, w is negative and ∆E is negative.

Section 9.4 If the volume of the system does not change, the heat transferred to or from a system
is the energy change of that system.

Section 9.4 If the pressure of the system does not change, the heat transferred to or from a system
is the enthalpy change of that system.

Section 9.4 When reactions are performed in an open container, such as a coffee-cup calorimeter,
the pressure (= atmospheric pressure) does not change and qP = ∆H; in a closed
container, such as a bomb calorimeter, the volume (= volume of the bomb) does not
change and q qx = ∆E. Even in an open container, unless a gas is involved in the
reaction, volume changes are usually negligible and ∆H ≅ ∆E.

Section 9.5 The states of reactants and products are important in determining an energy change
or enthalpy change for a reaction. The energy change will be different for a reaction
producing a product as a liquid (with lower energy) versus producing the same
product as a gas (with higher energy).

Section 9.5 Standard conditions as defined for thermodynamics (P = 1 atm; T = 298.15 K) are
different from standard conditions as defined for gas laws (P = 1 atm; T = 273.15 K).

Section 9.6 Endothermic means heat flows into a system and ∆H > 0. Exothermic means heat
flows out of a system and ∆H < 0.

Section 9.6 Temperature does not change during a change of state; hence, ∆Hfusion for water refers
to H2O(s, 0oC) → H2O(l, 0oC) and ∆Hvap for water refers to H2O(l, 100oC) → H2O(g,
100oC).

Section 9.7 Just as density provides a link between mass and volume, heat capacity links heat
flow and temperature change, allowing the three variables to be interconverted.

Section 9.7 The amount of heat transferred and, therefore, the temperature change depend on the
amount of substance involved. Specific heat is heat capacity per gram of substance
77
 Chapter 9—Thermochemistry: Chemical Energy

and has units of J/(g⋅oC); molar heat capacity is heat capacity per mole of substance
and has units J/(mol⋅oC).

Section 9.7 Specific heat and molar heat capacity are intensive properties that depend on the state
of the substance.

Section 9.8 Students have already employed Hess’s law when performing Born-Haber cycle
calculations.

Section 9.8 When an equation is reversed, ∆H must be multiplied by –1. When an equation is
multiplied by a coefficient, ∆H must be multiplied by the same coefficient.

Section 9.9 Remind students to multiply the heat of formation of each substance by its coefficient
in the chemical equation and also to multiply the standard heat of formation of each
product by –1.

Section 9.10 Bond dissociation energies are defined for isolated, gaseous-state species. Other
factors must be considered when dealing with condensed-state systems.

Section 9.10 Reactant bonds are broken and product bonds are formed: ∆Ho = D(reactant bonds
broken) – D(product bonds formed). Students should not confuse this equation for
that used for heats of formation: ∆Ho = ∆Hof(products) – ∆Hof(reactants), in which
products and reactants appear on the opposite side of the minus sign.

Section 9.10 Electron-dot structures should be drawn for each reactant and product to see the
number of each type of bond being broken and formed. These numbers must also be
multiplied by the coefficients in the balanced chemical equation.

Section 9.12 Another way to introduce entropy is to use a spontaneous process for which ∆H = 0,
such as the mixing of two ideal gases.

Section 9.13 ∆H has units of kJ, ∆S has much smaller units of J/K. Thus, reaction spontaneity as
measured by ∆G = ∆H –T∆S is usually dominated by ∆H except at high temperatures
or when the reaction results in an increase in the number of moles of gaseous
products.

Lecture/Laboratory Demonstration References

Section 9.6 Bassam Z. Shakhashiri, “Endothermic Reactions of Hydrated Barium Hydroxide and
Ammonium Salts,” Chemical Demonstrations, A Handbook for Teachers of
Chemistry, Vol. 1 (The University of Wisconsin Press, Madison, 1983), pp. 10-12.

Section 9.7 Bassam Z. Shakhashiri, “Boiling Water in a Paper Cup: Heat Capacity of Water,”
Chemical Demonstrations, A Handbook for Teachers of Chemistry, Vol. 3 (The
University of Wisconsin Press, Madison, 1989), pp. 239-241.

Section 9.7 Lee R. Summerlin, Christie L. Borgford, and Julie B. Ealy, “A Chemical Hand
Warmer,” Chemical Demonstrations, A Sourcebook for Teachers, Vol. 2 (American
Chemical Society, Washington, DC, 1988), pp. 101-102.

78
 Chapter 9—Thermochemistry: Chemical Energy

Section 9.7 Bassam Z. Shakhashiri, “Chemical Cold Pack,” Chemical Demonstrations, A

Handbook for Teachers of Chemistry, Vol. 1 (The University of Wisconsin Press,
Madison, 1983), pp. 8-9.

Section 9.7 Bassam Z. Shakhashiri, “Heat of Neutralization,” Chemical Demonstrations, A

Handbook for Teachers of Chemistry, Vol. 1 (The University of Wisconsin Press,
Madison, 1983), pp. 15-16.

Section 9.7 Lee R. Summerlin and James L. Ealy, Jr., “Endothermic Reaction: Ammonium
Nitrate,” Chemical Demonstrations, A Sourcebook for Teachers, Vol. 2 (American
Chemical Society, Washington, DC, 1988), p. 65.

Section 9.11 Lee R. Summerlin, Christie L. Borgford, and Julie B. Ealy, “Making Canned Heat,”
Chemical Demonstrations, A Sourcebook for Teachers, Vol. 2 (American Chemical
Society, Washington, DC, 1988), pp. 111-112.

Literature References
Section 9.7 John J. Fortman, “Analogical Demonstrations,” J. Chem. Educ., Vol. 69, 1992, 323-
324.

Section 9.7 Charles M. Wynn, Sr., “Heat Flow vs. Cash Flow: A Banking Analogy,” J. Chem.
Educ., Vol. 74, 1997, 397-398.

Section 9.7 Brother Thomas McCullogh, “A Specific Heat Analogy,” J. Chem. Educ., Vol. 57,
1980, 896.

Section 9.7 Doris R. Kimbrough, “Heat Capacity, Body Temperature and Hypothermia,” J.
Chem. Educ., Vol. 75, 1998, 48-49.

Section 9.11 Donald J. Wink, “The Conversion of Chemical Energy. Part 1. Technological
Examples,” J. Chem. Educ., Vol. 69, 1992, 108-111.

Section 9.11 Gustav P. Dinga, “Hydrogen: The Ultimate Fuel and Energy Carrier,” J. Chem.
Educ., Vol. 65, 1988, 688-691.

Section 9.11 Israel Dostrovsky, “Chemical Fuels from the Sun,” Scientific American., Vol. 265,
1991, pp. 102-107.

Section 9.11 Harold H. Schobert, “The Geochemistry of Coal. Part II: The Components of Coal,”
J. Chem. Educ., Vol. 66, 1989, 290-293.

Section 9.12 John J. Fortman, “Pictorial Analogies III: Heat Flow, Thermodynamics, and
Entropy,” J. Chem. Educ., Vol. 70, 1993, 102-103.

Media References

Section 9.3 Expansion Work activity from the Instructor Resource DVD

Section 9.3 Work of Gas Expansion movie from the Instructor Resource DVD

79
 Chapter 9—Thermochemistry: Chemical Energy

Section 9.4 Signs for q and w activity from the Instructor Resource DVD

Section 9.4 Heat Transfer activity from the Instructor Resource DVD

Section 9.6 Enthalpies of Chemical Change activity from the Instructor Resource DVD

Section 9.6 Thermite movie from the Instructor Resource DVD

Section 9.6 Changes of State movie from the Instructor Resource DVD

Section 9.9 Formation of Aluminum Bromide movie from the Instructor Resource DVD

Section 9.10 Bond Dissociation activity from the Instructor Resource DVD

Section 9.12 Airbags movie from the Instructor Resource DVD

Section 9.12 Spontaneous Process activity from the Instructor Resource DVD

Section 9.13 Formation of Water movie from the Instructor Resource DVD

Section 9.13 Formation of Water activity from the Instructor Resource DVD

80