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Practice Exercises
∆E = w + q = 0
0 = –154 + q
(The energy is converted into heat; since the heat does not leave the system the temperature increases.)
19.5 ∆S should be negative since the reaction moves from great movement of ions in solution to less movement
in the solid.
19.6 (a) ∆S is negative since the products have a lower entropy, i.e. a lower freedom of movement.
(b) ∆S is positive since the products have a higher entropy, i.e. a higher freedom of movement.
19.7 (a) ∆S is negative since there are less gas molecules. (The product is also more complex, indicating
an increase in order.)
(b) ∆S is negative since there are less gas molecules. (The product is also more complex, indicating
an increase in order.)
19.8 (a) ∆S is negative since there is a change from a gas phase to a liquid phase. (The product is also
more complex, indicating an increase in order.)
(b) ∆S is negative since there are less gas molecules. (The product is also more complex, indicating
an increase in order.)
(c) ∆S is positive since the particles go from an ordered, crystalline state to a more disordered,
aqueous state.
1 3
19.9 N2(g) + H2(g) NH3(g)
2 2
1 3
∆Sof = [ SNH3 (g) ] – [ SoN2 (g) + SoH2 (g) ]
o
2 2
465
Chapter 19
The temperature is 25.0 + 273.15 = 298.15 K, and the calculation of ∆G° is as follows: ∆G° = ∆H° – T∆S°
= –1644 kJ – (298.15 K)(–0.543 kJ/K) = –1482 kJ
466
Chapter 19
25
C8H18(l) + O2(g) 8CO2(g) + 9H2O(l)
2
25
∆G°rxn = {8∆Gf°[CO2(g)] + 9∆Gf°[H2O(l)]} – {∆Gf°[C8H18(l)] + ∆Gf°[O2(g)]}
2
25
∆G°rxn = {8 mol × (–394.4 kJ mol–1) + 9 mol × (–237.2 kJ mol–1)} – {1 mol × (+17.3 kJ mol–1) + mol ×
2
(0 kJ mol–1)}
G°rxn = –5304.1 kJ
For 125 g C8H18:
1 mol C8 H18
mol C8H18 = 125 g C8H18 = 1.09 mol C8H18
114.26 g C8 H18
Maximum work:
(5304.1 kJ mol–1)(1.09 mol C8H18) = 5803 kJ
The octane is a better fuel on both a per gram and per mole basis.
19.16 The maximum amount of work that is available is the free energy change for the process, in this case, the
standard free energy change, ∆G°, since the process occurs at 25 °C.
4Al(s) + 3O2(g) 2Al2O3(s)
467
Chapter 19
This calculation conforms to the reaction as written. This means that the above value of ∆G° applies to the
equation involving 4 mol of Al. The conversion to give energy per mole of aluminum is then: –3152.8
kJ/4 mol Al = –788 kJ/mol
The maximum amount of energy that may be obtained is thus 788 kJ.
∆H o
19.17 T ≈
∆So
1000 J
∆Ho = 21.7 kJ mol–1 3
= 21.7 × 10 J
1 kJ
21.7 × 103 J
239.9 K ≈
∆So
o –1
∆S = 90.5 J K
19.18 For the vaporization process in particular, and for any process in general, we have:
∆G = ∆H – T∆S
If the temperature is taken to be that at which equilibrium is obtained, that is the temperature of the boiling
point (where liquid and vapor are in equilibrium with one another), then we also have the result that ∆G is
equal to zero:
∆G = 0 = ∆H – T∆S, or Teq = ∆H/∆S
We know ∆H to be 60.7 kJ/mol; we need the value for ∆S in units kJ mol–1 K–1:
∆G° is positive, the reaction is not spontaneous, and we do not expect to see products formed from
reactants.
468
Chapter 19
PN O
19.23 ∆G = ∆G o298 + RT ln 2 42
PNO
2
0.598 atm
( )
∆G = −5.40 × 103 J mol −1 + 8.314 J mol−1 K −1 ( 298 K ) ln
( 0.260 atm )2
∆G = 0 J mol–1 = 0 kJ mol–1
The system is at equilibrium, so that the reaction will not move.
PN O
∆G = ∆G o + RT ln 2 4
PNO
2
0.25 atm
( )
= − 5.40 × 103 J mol−1 + 8.314 J mol−1 K −1 ( 298 K ) ln
( 0.60 atm )2
(
= − 5.40 × 103 J mol−1 + −9.03 × 10 2 J mol−1 )
3 −1
= − 6.30 × 10 J mol
Since ∆G is negative, the forward reaction is spontaneous and the reaction will proceed to the right.
469
Chapter 19
Kp = 0.26
∆ H (Bond Formation)
0
∆ H (atoms)
f
The heat of formation of the gaseous reactants is endothermic, and therefore positive.
The heat of formation of the gaseous reactants is endothermic, and therefore positive.
470
Chapter 19
The heat of formation of the gaseous reactants is endothermic, and therefore positive.
The heat of formation of the gaseous reactants is endothermic, and therefore positive.
Benzene bonding is neither single nor double bonding between carbon atoms but we will approximate the
bonding as 3 single C-C bonds and 3 double C-C bonds.
471
Chapter 19
Review Questions
19.1 The term thermodynamics is meant to convey the two ideas of thermo (heat) and dynamics (motion),
namely movement or transfer of heat.
The first law of thermodynamics states that the internal energy may be transferred as heat or work, but it
cannot be created or destroyed. The change in internal energy of a system is the sum of two terms, the
amount of energy the system gains from heat transfer and the amount of energy the system gains from work
transfer: ∆E = q + w. ∆E is positive is energy flows into a system and negative if energy flows out of a
system.
19.3 If we refer to the equation in the answer to Review Question 19.2, we can see that if Efinal is larger than
Einitial, then ∆E must be positive, by definition. Thus, ∆E for an endothermic process is positive.
19.4 ∆E is the change in internal energy, which is positive for an endothermic process. Heat, q, is the absorbed
by the system during the process, and it has a positive sign if the system absorbs heat during the process.
Work, w, is done on the system by the surroundings during the process, and it has a negative sign if the
system does work on the surroundings, whereas it has a positive sign if the surroundings do work on the
system during the process.
19.5 A state function is a thermodynamic quantity whose value is determined only by the state of the system
currently, and is not determined by a system's prior condition or history. A change in a state function is the
same regardless of the path that is used to arrive at the final state from the initial state. That is, changes in
state function quantities are path–independent. In the statement of the first law, only ∆E is a state function.
19.6 ∆E is the heat of reaction at constant volume, and applies, for instance, to reactions performed in closed
vessels such as bomb calorimeters. ∆H is the heat of reaction at constant pressure.
The last result is the Newton · meter, or a force times a distance. By definition, a force of 1 N operating
over a distance of 1 meter is the quantity 1 joule. Thus, the quantity P × ∆V has the units of energy,
namely joules.
19.8 Since the quantity P∆V is negative (corresponding to a decrease in volume), ∆E must be a smaller negative
quantity than ∆H. ∆E is a smaller negative quantity than ∆H because, if the change is carried out at
constant pressure, some energy is gained by the system as volume contracts.
19.9 The most negative value of ∆E will have the most energy released.
(a) Compressing the spring: energy is added to the system: w > 0
Heating the spring: energy is added to the system: q > 0
(b) Expanding the spring: energy is removed from the system: w < 0
Cooling the spring: energy is removed from the system: q < 0
(c) Compressing the spring: energy is added to the system: w > 0
Cooling the spring: energy is removed from the system: q < 0
(d) Expanding the spring: energy is removed from the system: w < 0
Heating the spring: energy is added to the system: q > 0
In case (b), q < 0 and w < 0 so ∆E is the most negative
472
Chapter 19
19.10 A spontaneous change, in thermodynamic terms, is one for which the sign of ∆G is negative. It is a process
that occurs by itself, without continued outside assistance. Kinetics plays no role in determining
spontaneity.
19.11 Student dependent answer. Examples of spontaneous changes may include: leaves falling from a tree, open
soda cans losing their carbonation, food molding in the refrigerator, dorm rooms becoming messy.
Examples of non–spontaneous changes may include: dorm rooms becoming neat and tidy, class notes
becoming organized, leaves being raked into a pile.
19.12 Student dependent answer. For the examples given above all of the non–spontaneous changes are
endothermic, they all require the surroundings expenditure of energy. The spontaneous changes are all
exothermic except, perhaps, the dorm room becoming messy. This change may be either exothermic or
endothermic.
19.13 A change that is characterized by a negative value for ∆H tends to be spontaneous. The only situation
where this is not true is that in which the value of the product T∆S is sufficiently negative to make the
quantity ∆G = ∆H – T∆S become positive.
19.14 Spontaneous processes tend to proceed from states of low probability to states of higher probability.
19.15 The ammonium and nitrate atoms are in a highly ordered geometry in the crystalline NH4NO3 sample.
When NH4NO3 dissolves, the NH4+ and NO3– ions become randomly dispersed throughout the solvent. The
increase in randomness that attends the dissolving of the solid is responsible for the process being
favorable, or spontaneous, in spite of the fact that the enthalpy change is endothermic.
19.16 Entropy is a measure of the number of microstates of a system. An equivalent statement is that entropy is a
measure of the statistical probability of a system.
19.17 Entropy is a measure of the randomness of a system, an increase in randomness corresponds to an increase
in entropy.
(a) An increase in temperature allows the atoms and molecules to move more rapidly,
therefore there is an increase in entropy.
(b) A decrease in volume limits the space that the molecules and atoms have to move in,
therefore there is a decrease in entropy.
(c) Changing a liquid to a solid limits the motion of the molecules; therefore there is a
decrease in entropy.
(d) Dissociating into individual atoms increases the entropy because there are more particles.
19.19 The statistical probability of a system in a given state, relative to all the other states, is the same regardless
of how the system happened to have been formed.
19.20 The entropy of the universe increases when a spontaneous event occurs.
19.21 A spontaneous event occurs when ∆G is negative. Since ∆G = ∆H – T∆S, even if the entropy is negative
for a process, the enthalpy factor, ∆H may be negative enough at a given temperature to allow the overall
change in free energy to be negative.
19.22 This is the statement that the entropy of a perfect crystalline solid at 0 K is equal to zero: S = 0 at 0 K.
19.23 The entropy of a mixture must be higher than that of two separate pure materials, because the mixture is
guaranteed to have a higher degree of disorder. Said another way, a mixture is more disordered than either
of its two separate components. Only a pure substance can have an entropy of zero, and then only at 0 K.
473
Chapter 19
19.24 Entropy increases with increasing temperature because vibrations and movements within a solid lead to
greater disorder at the higher temperatures. Melting especially produces more disorder and vaporization
even more.
19.25 No, glass is an amorphous solid that is really a mixture of different substances so it is not a perfect
crystalline solid and does not have an entropy value of 0 at 0K.
19.26 ∆G = ∆H – T∆S
19.27 (a) A change is spontaneous at all temperatures only if ∆H is negative and ∆S is positive.
(b) A change is spontaneous at low temperatures but not at high temperatures only if ∆H is negative
and ∆S is negative.
(c) A change is spontaneous at high temperatures but not at low temperatures only if ∆H is positive
and ∆S is positive.
19.29 The value of ∆G is equal to the maximum amount of work that may be obtained from any process.
19.30 A reversible process is one in which the driving force of the process is nearly completely balanced by an
opposing force. The situation is a bit esoteric, since no process can be run in a completely reversible
manner. Nevertheless, the closer one obtains to reversibility, the more efficient the system becomes as a
source of the maximum amount of useful work that can be achieved with the process.
19.31 The slower that the energy extraction is performed, the greater is the total amount of energy that can be
obtained. This is the same as saying that the most energy is available from a process that occurs reversibly.
19.32 As with other processes that are not carried out in a reversible fashion, the energy is lost to the environment
and becomes unavailable for use. In addition, much of the energy is lost as heat which is used to maintain
our body temperature.
19.33 A truly reversible process would take forever to occur. Thus, if we can observe an event happening, it
cannot be a truly reversible one.
19.35 The process of bond breaking always has an associated value for ∆H that is positive. Also, since bond
breaking increases disorder, it always has an associated value for ∆S that is positive. A process such as
this, with a positive value for ∆H and a positive value for ∆S, becomes spontaneous at high temperatures.
19.36 Before the heat transfer, the molecules in the hot object vibrate and move more violently than do those of
the cooler object. When in contact with one another, the objects transfer heat through collisions, and
eventually, some of the kinetic energy of the molecules in the hot object is transferred to the molecules of
the cool object. This process of energy transfer continues until the objects have the same temperature. The
heat transfer is spontaneous because the scattering of kinetic energy among the molecules of both objects is
a process with a positive value for its associated ∆S.
19.38 Although a reaction may have a favorable ∆G, and therefore be a spontaneous reaction in the
thermodynamic sense of the word, the rate of reaction may be too slow at normal temperatures to be
observed.
19.39 As the temperature is raised, °G' will become less negative, if ∆H° is negative and ∆S° is negative.
Accordingly, less product will be present at equilibrium.
474
Chapter 19
19.43 The amount of energy needed to break all the chemical bonds in one mole of gaseous molecules to give
gaseous atoms.
19.44 It is easy to see why the conversion of a solid or liquid element to gaseous atoms is an endothermic process.
In the case of elements which exist naturally as gases, most are polyatomic (the exception are the noble
gases). To convert these elements to gaseous atoms will require an input of energy as bonds need to be
broken.
19.45 Heat of formation is defined as the amount of energy needed to form the compound from its elements in
their most stable state. C2(g) is not the naturally occurring state of carbon.
Review Problems
The overall process is endothermic, meaning that the internal energy of the system increases. Notice that
both terms, q and w, contribute to the increase in internal energy of the system; the system gains heat (+q)
and has work done on it (+w).
19.47 ∆E = q + w
–1785 J = 945 J + w
w = –2730 J
Since w is defined to be the work done on the system by the surroundings, then in this case, a negative
amount of work is done on the system by the surroundings. The system, in fact, does work on the
surroundings.
19.48 work = P × ∆V
The total pressure caused by the hand pump:
P = 30.0 lb/in2
19.49 This is a reaction that produces 1 mol of a single gaseous product, CO2. Furthermore, this mole of gaseous
product forms from nongaseous materials. The volume that will be occupied by this gas, once it is formed,
can be found by application of Charles' Law: 22.4 L × 298 K/273 K = 24.5 L
475
Chapter 19
∆E = ∆H° – ∆nRT
∆E = 24.58 kJ – (+2 mol)(8.314 J/mol K)(10–3 kJ/J)(298 K) = 19.6 kJ
∆E = ∆H° – ∆nRT
∆E = –178 kJ – (–1)(8.314 J/mol K)(10–3 kJ/J)(298 K) = –175 kJ
19.51 We proceed as in the answer to Review Problem 19.50, using the data supplied in Appendix C.
(a) 2C2H2(g) + 5O2(g) 4CO2(g) + 2H2O(g)
∆H° = {2 ∆Hof [H2O(g)] + 4 ∆Hof [CO2(g)]} – {5 ∆Hof [O2(g)] + 2 ∆Hof [C2H2(g)]}
∆H° = {2 mol × (–241.8 kJ/mol) + 4 mol × (–393.5 kJ/mol)}
– {5 mol × (0.0 kJ/mol) + 2 mol × (226.75 kJ/mol)}
∆H° = –2511.1 kJ
476
Chapter 19
∆E = ∆H° – ∆nRT
∆E = –1663.4 kJ – (2 mol)(8.314 J/mol K)(10–3 kJ/J)(298 K)
∆E = –1668 kJ
∆E = ∆H° – ∆nRT
∆E = 176.9 kJ – (2 mol)(8.314 J/mol K)(10–3 kJ/J)(298 K)
∆E = 171.9 kJ
∆E = ∆H° – ∆nRT
∆E = –1657.8 kJ – (2 mol)(8.314 J/mol K)(10–3 kJ/J)(298 K)
∆E = –1662.8 kJ
19.52 ∆H = ∆E + ∆ngasRT
∆E = ∆H – ∆ngasRT
∆H = –163.14 kJ
∆ngas = 3 mol – 2 mol = 1 mol
R = 8.314 J mol–1 K–1
T = 25 °C + 273 K = 298 K
For 195 g N2O, first calculate the number of moles of N2O and then how many kJ of energy will be
released for that many moles of N2O
∆E = –163.14 kJ – (1 mol)(8.314 × 10–3 kJ mol–1 K–1)(298 K)
∆E = –165.62 kJ
1mol N 2 O
mol N2O = 195 g = 4.43 mol N2O
44.02 g N 2 O
−165.62 kJ
Amount of Energy = 4.43 mol N2O = –367 kJ
2 mol N 2 O
For T = 212 °C
T = 212 °C + 273 K = 485 K
∆E = –163.14 kJ – (1 mol)(8.314 × 10–3 kJ mol–1 K–1)(485 K)
∆E = –163.14 kJ –4.03 kJ
∆E217 °C = –167.17 kJ for 2 moles of N2O
13
19.53 C4H10(g) + O2(g) 4CO2(g) + 5H2O(g)
2
477
Chapter 19
Find the moles of C4H10 at the first set of pressure, volume, and temperature data, then find the moles of the
CO2 and H2O resulting from the reaction. Finally, find the new volume of the products.
PV = nRT
( 2.00 atm )(10.0 L )
mol C4H10 = = 0.826 mol C4H10
( 0.0821 L atm mol−1 K −1 ) ( 295 K )
4 mol CO 2
mol CO2 = ( 0.826 mol C 4 H10 ) = 3.30 mol CO2
1 mol C 4 H10
5 mol H 2 O
mol H2O = ( 0.826 mol C 4 H10 ) = 4.13 mol H2O
1 mol C 4 H10
total moles of product = 3.30 mol CO2 + 4.13 mol H2O = 7.43 mol
initial volume =
( )
( 0.826 mol) 0.0821 L atm mol−1 K −1 ( 305 K )
= 20.7 L
1.00 atm
final volume =
( )
( 7.43 mol) 0.0821 L atm mol−1 K −1 ( 305 K )
= 186 L
1.00 atm
w = –P∆V
w = –(1.00 atm)(186 L – 20.7 L) = 165 L atm
101.325 J 1 kJ
In kilojoules: 165 L atm = 16.7 kJ
1 L atm 1000 J
19.54 In general, we have the equation: ∆H° = (sum ∆Hf [products]) – (sum ∆Hf [reactants])
(a) ∆H° = { ∆Hof [CaCO3(s)]} – { ∆Hof [CO2(g)] + ∆Hof [CaO(s)]}
∆H° = {1 mol × (–1207 kJ/mol)} – {1 mol × (–393.5 kJ/mol) + 1 mol × (–635.5 kJ/mol)}
∆H° = –178 kJ ∴ favored.
(c) ∆H° = { ∆Hof [Fe2O3(s)] + 3 ∆Hof [Ca(s)]} – {2 ∆Hof [Fe(s)] + 3 ∆Hof [CaO(s)]}
∆H° = {1 mol × (–822.2 kJ/mol) + 3 mol × (0.0 kJ/mol)}
– {2 mol × (0.0 kJ/mol) + 3 mol × (–635.5 kJ/mol)}
∆H° = +1084.3 kJ ∴ not favorable from the standpoint of enthalpy alone.
(b) ∆H° = {2 ∆Hof [H2O(g)] + 4 ∆Hof [CO2(g)]} – {5 ∆Hof [O2(g)] + 2 ∆Hof [C2H2(g)]}
∆H° = {2 mol × (–241.8 kJ/mol) + 4 mol × (–393.5 kJ/mol)}
– {5 mol × (0.0 kJ/mol) + 2 mol × (226.75 kJ/mol)}
∆H° = –2512 kJ ∴ favored from the standpoint of enthalpy alone.
478
Chapter 19
19.58 (a) negative – since the number of moles of gaseous material decreases.
(b) negative – since the number of moles of gaseous material decreases.
(c) negative – since the number of moles of gas decreases.
(d) positive – since a gas appears where there formerly was none.
19.59 (a) ∆S is positive since randomness in a gas is higher than that in a solid.
(b) ∆S is negative. There are fewer moles of gases among the products.
(c) ∆S is negative since gaseous material (which is highly random) is replaced by a solid (which is
highly ordered).
(d) ∆S is negative since the relatively random liquid reactant disappears in a process that makes only a
solid.
479
Chapter 19
19.62 The entropy change that is designated ∆Sf is that which corresponds to the reaction in which one mole of a
substance is formed from elements in their standard states. Since the value is understood to correspond to
the reaction forming one mole of a single pure substance, the units may be written either J K–1 or J
mol–1 K–1.
480
Chapter 19
= –311.0 J/K.mol
19.63 The entropy change that is designated ∆Sf is that which corresponds to the reaction in which one mole of a
substance is formed from elements in their standard states. Since the value is understood to correspond to
the reaction forming one mole of a single pure substance, the units may be written
either J K–1 or J mol–1 K–1.
19.66 The quantity ∆G f applies to the equation in which one mole of pure phosgene is produced from the
naturally occurring forms of the elements:
C(s) + 1/2O2(g) + Cl2(g) COCl2(g), ∆G f = ?
We can determine if we can find values for ∆Hf and ∆Sf , because:
s
∆G° = ∆H° – T∆S°
The value of ∆Sf is determined using S° for phosgene in the following way:
∆Sof = {S°[COCl2(g)]} – {S°[C(s)] + 1/2S°[O2(g)] + S°[Cl2(g)]}
481
Chapter 19
This value agrees well with the value listed in Appendix C2.
482
Chapter 19
19.70 Multiply the reverse of the second equation by 2 (remembering to multiply the associated free energy
change by –2), and add the result to the first equation:
19.71 Add the reverse of the first equation to the second equation plus twice the third equation:
19.72 The maximum work obtainable from a reaction is equal in magnitude to the value of ∆G for the reaction.
Thus, we need only determine ∆G° for the process:
Next, we determine the amount of work available from the combustion of 64.0 g of CH4:
483
Chapter 19
1 mol CH 4 −800.8 kJ
kJ = ( 64.0 g CH 4 )
3
= − 3.19 × 10 kJ
16.043 g CH 4 1 mol CH 4
19.74 At equilibrium, ∆G = 0 = ∆H – T∆S
Teq = ∆H/∆S, and assuming that ∆S is independent of temperature, we have:
Teq = (31.4 × 103 J mol–1) ÷ (94.2 J mol–1 K–1) = 333 K
19.78 The reaction is spontaneous if its associated value for ∆G° is negative.
∆G° = (sum ∆G of [products]) – (sum ∆G of [reactants])
∆G° = { ∆G of [HC2H3O2(l)] + ∆G of [H2O(l)] + ∆G of [NO(g)] + ∆G of [NO2(g)]}
– { ∆G of [C2H4(g)] + ∆G of [HNO3(l)]}
∆G° = {1 mol × (–392.5 kJ/mol) + 1 mol × (–237.2 kJ/mol)
+ 1 mol × (86.69 kJ/mol) + 1 mol × (51.84 kJ/mol)}
– {1 mol × (68.12 kJ/mol) + 1 mol × (–79.91 kJ/mol)}
∆G° = –479.4 kJ
19.79 We first balance each equation, and then calculate a value of ∆G°. If ∆G° is a negative number, then the
reaction is spontaneous.
484
Chapter 19
1
19.80 PCl3(g) + O 2( g ) → POCl3(g)
2
(b) The ∆G of for H2O2(g) is not given in Appendix C. The value was found in the Handbook of
Chemistry and Physics, 84th Edition, 2003 – 2004, David R. Lide, Ed., CRC Press, New York.
∆G° = {2 × ∆G of [NO2(g)] + 8 × ∆G of [H2O(g)]}
– {1 × ∆G of [N2H4(g)] + 6 × ∆G of [H2O2(g)]}
∆G° = [2 mol × (51.84 kJ/mol) + 8 mol × (–228.6 kJ/mol)]
– [1 mol × (159.3 kJ/mol) + 6 mol × (–105.6 kJ/mol)]
∆G° = –1250.8 kJ = –1.2508 × 106 J
–1.2508 × 106 J = –RTlnKp = –(8.314 J/K mol)(298 K) × lnKp
lnKp = 5.048 × 102 ∴ Kp = 1.70 × 10219
This is rocket fuel!
485
Chapter 19
We start by calculating the reaction quotient, Q. Be sure to determine the pressure of the gases using the
ideal gas law.
( )( )
3.8 × 10−3 mol 0.0821 L atm ( 673 K )
mol K
1.50 L
Q= = 0.117
(
( 0.040 mol ) 0.0821
mol K (
L atm
) (
673 K ) ( 0.022 mol ) 0.0821 mol
L atm
K ) ( 673 K )
1.50 L 1.50 L
Since the value of Q is larger than the value of Kp, the system must shift to the left in order to reach
equilibrium.
19.86 If ∆G° = 0, Kc = 1. If we start with pure products, the value of Q will be infinite (there are zero reactants)
and, since Q > Kc, the equilibrium will shift towards the reactants, i.e., the pure products will decompose to
their reactants.
NH3 N + 3H
486
Chapter 19
The enthalpy of atomization of NH3 is thus three times the average N–H single bond energy:
3 × 388 kJ/mol = 1.16 × 103 kJ/mol
19.89 The energy released during the formation of 1 mol of acetone is equal to the sum of all of the bond energies
in the molecule:
for the eight C—H bonds: 412 kJ/mol × 8 mol C—H bonds
for the two C—C bonds: 348 kJ/mol × 2 mol C—C bonds
for the one C=O bond: 743 kJ/mol × 1 mol C=O bonds
for the two C–O bonds: 360 kJ/mol × 2 mol C–O bonds
Adding the above contributions we get 5.46 × 104 kJ released per mole of acetone formed.
19.90 The heat of formation for ethanol vapor describes the following change:
2C(s) + 3H2(g) +1/2O2(g) C2H5OH(g)
This can be arrived at by adding the following thermochemical equations, using data from Table 19.3:
3H2(g) 6H(g) ∆H1° = (6)217.89 kJ = 1307.34 kJ
2C(s) 2C(g) ∆H2° = (2)716.67 kJ = 1,433.34 kJ
1/2O2(g) O(g) ∆H3° = (1)249.17 kJ = 249.17 kJ
6H(g) + 2C(g) + O(g) C2H5OH(g) ∆H4° = x
∆H°atom = 3225.2 kJ
The sum of all the bond energies in the molecule should be equal to the atomization energy:
19.91 ∆Hf [C2H4(g)] refers to the enthalpy change under standard conditions for the following reaction:
We can arrive at this net reaction in an equivalent way, namely, by vaporizing all of the necessary elements
to give gaseous atoms, and then allowing the gaseous atoms to form all of the appropriate bonds. The
overall enthalpy of formation by this route is numerically equal to that for the above reaction, and,
conveniently, the enthalpy changes for each step are available in either Table 19.3 or Table 19.4:
∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)
∆Hf [C2H4(g)] = 52.284 kJ/mol = [2 × 716.7 + 4 × 218.0] – [4 × 412 + C=C] from which we can calculate
the C=C bond energy: 605 kJ/mol.
487
Chapter 19
19.93 ∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)
∆Hf [H2S(g)] = –20.15 kJ/mol = [277.0 + 2 × 218.0] – [2 × H–S]
H–S = (20.15 + 277.0 + 2 × 218.0) ÷ 2 = 366.6 kJ/mol
19.95 ∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)
∆Hf [SF4(g)] = [277.0 + 4 × 79.14] – [4 × 308.0]
= –638.4 kJ/mol
The % difference is [(718.4 – 638.4) ÷ 718.4] × 100% = 11 %
19.96 ∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)
19.97 ∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)
∆Hf [CCl4(g)] = [716.67 + 4 × 121.47] – [4 × 338] = –149 kJ/mol
19.98 The heat of formation of CF4 should be more exothermic than that of CCl4 because more energy is released
on formation of a C—F bond than on formation of a C—Cl bond. Also, less energy is needed to form
gaseous F atoms than to form gaseous Cl atoms.
19.99 The computed value for ∆Hf for benzene is likely to be larger than the experimentally measured value. The
reason for the difference is that the computation neglects the stabilization provided by the high degree of
conjugation/resonance.
Additional Exercises
or
8.314 J mol−1 K −1
1 L atm × = 101.325 J
0.0821 L atm mol−1 K −1
488
Chapter 19
19.101 w = –P∆V
P = 1 atm
∆V = 8.00 L – 4.00 L = 4.00 L
w = –(1 atm)(4.00 L) = –4.00 L atm
In joules:
101.325 J
–4.00 L atm = –405 J
1 L atm
19.102 Under reversible conditions, the expansion of an ideal gas produces the maximum amount of work that can
be obtained from the change. Such a situation cannot be accomplished by any real process. In an ideal gas,
the gas particles are non-interacting. In a real gas, the interaction between the individual particles must be
overcome so that the gas may expand. It requires an input of energy to overcome these attractive forces.
19.103 The expansion of a real gas is not reversible, and not all of the free energy change for the process is
converted to work as the gas expands. Some of the energy must be used to overcome the intermolecular
forces of attraction that exist between molecules. In an ideal gas, the particles are assumed to be non-
interacting and this energy loss is not a concern. See 19.102
19.105 We can calculate the work of the expanding gas (P∆V) if we can calculate the change in volume ∆V. Since
the initial volume is given (4.50 L), we need only to calculate the final volume. For this, it is first
necessary to determine the value of n, the number of moles of gas.
PV (3.50 atm)(4.50 L)
n= = = 0.644 mol
RT ( L atm
0.0821 mol K )
(298 K)
V2 =
nRT
=
(
(0.644 mol) 0.0821 L atm
mol K ) (298 K) = 15.8 L
P2 1 atm
∆V = (15.8 L − 4.50 L) = 11.3 L
The work of gas expansion against a constant pressure of 1 atm is then given by the quantity –P∆V: w = –
(1 atm)(11.3 L) = –11.3 L atm
19.106 As in exercise 19.105, we solve for the volume after the first expansion to a pressure of 2 atm:
V2 =
nRT
=
(
(0.817 mol) 0.0821 L atm
mol K ) (298 K) = 10.0 L
P2 2 atm
19.107 First, review the information provided. Since the salt dissolved, the process is spontaneous, and the sign
for ∆G is negative. The temperature went down indicating that this is an endothermic process and ∆H must
489
Chapter 19
be positive. Dissolving the solid salt increases the disorder of the system which indicates ∆S is positive.
The general equation from which we must work is ∆G = ∆H – T∆S. Using this equation, the magnitude of
T∆S must be larger than the magnitude of ∆H in order to obtain a negative value for ∆G. However, the
magnitude of ∆H is almost certainly larger than that of ∆S as can be appreciated from the fact that ∆S˚
values are given in J and those of ∆H˚f are given in kJ.
19.110 The value for ∆G° is given in the problem, and values for the free energy of formation of all other reactants
and products can be obtained in Appendix C2.
490
Chapter 19
∆G1173
o
= –25,600 J = –25.6 kJ
2x = 5% of 1.00 = 0.05
x = 0.025
[ClNO] = 0.95
[Cl2] = 0.025
[NO] = 0.05
[Cl2 ][ NO] [0.025][0.05]
2 2
K= = = 6.9 × 10–5
[ ClNO] [0.95]
2 2
∆G o298 = –RTlnK
∆G o298 = –(8.314 J mol–1 K–1)(298 K)(ln 6.9 × 10–5)
∆G o298 = 23,700 J = 23.7 kJ
ln K = 3.53
K = 34.2
K=
[ NO ] [ NO ] =
2 ( x )( x ) = 34.2
[ N O ][ O ] ( 0.06 − x )( 0.06 − x )
2 2
5.85 =
( x)
( 0.06 − x )
0.351 – 5.85x = x
0.351 = 6.85x
x = 0.0512
The percentage of N2O reacted is:
491
Chapter 19
0.0512
× 100% = 85.4%
0.06
19.115 The reaction is N2(g) 2N(g), ∆H° = 2 ∆Hf [N(g)] – ∆Hf [N2(g)]. Since the enthalpy of formation of
molecular nitrogen is defined as zero, the enthalpy change for this reaction and, consequently, the bond
energy of a nitrogen molecule, is simply two times the enthalpy of formation of atomic nitrogen.
472.68 kJ
Bond Energy = ( 2 mol N atoms ) = 945.36 kJ
mol N atoms
A similar argument holds true for oxygen:
249.17 kJ
Bond Energy = ( 2 mol O atoms ) = 498.34 kJ
mol N atoms
4x = 0.0743 M
x = 0.0186 M
[N2O] = 0.157 – 2(0.0186) = 0.120 M
[O2] = 0.0968–3(0.186) = 0.041 M
[NO2] = 0.0743 M
K=
[ NO ] 2
4
=
( 0.0743) 4
= 31
[ N O] [ O ] ( 0.120) 2 ( 0.041) 3
2 3
2 2
∆G° = –RTlnK
∆G° = –(8.314 J mol–1K–1)(298 K)(ln 31)
∆G° = –8.51 × 103 J mol–1
∆G° = –8.51 kJ mol–1
492
Chapter 19
Multi-Concept Problems
19.119 We need to calculate the amount of energy produced when one gallon of each of these fuels is burned;
0.7893 g ethanol 1 mole ethanol
(
mol ethanol = 3.78 × 103 mL ethanol )
1 mL ethanol 46.07 g ethanol
= 64.8 moles ethanol
−1299.8 kJ 4
kJ = (64.8 moles ethanol) = 8.42 × 10 kJ
1 mole ethanol
0.7025 g octane 1 mole octane
(
mol octane = 3.78 × 103 mL octane )
1 mL octane 114.23 g octane
= 23.2 moles octane
−5307 kJ 5
kJ = (23.2 moles octane) = 1.23 × 10 kJ
1 mole octane
In spite of the large number of moles of ethanol in one gallon of liquid, the energy produced from the
combustion of a gallon of octane is greater than the amount produced when one gallon of ethanol is burned.
19.120 Strong acids and bases are strong electrolytes. Therefore, the net ionic equation for the reaction of a strong
acid and strong base is given by:
Propionic acid is a weak acid, therefore the net ionic equation for its reaction with a strong base is:
If we reverse the first reaction (1) and combine it with the second reaction (2) we obtain the desired
ionization reaction and the enthalpy of ionization.
The entropy change for the reaction can be determined from the enthalpy of the reaction and the
equilibrium constant for propionic acid.
493
Chapter 19
A catalyst alters the kinetics of a reaction, increasing the rate so that equilibrium is achieved more quickly,
but does not shift the equilibrium. Therefore, this claim is false.
n = PV/(RT) = (1.00 atm x 117 m3 x 1000 L m-3)/(0.0821 L atm K−1 mol−1 x 273 K) = 5220 mol CH4
The reaction should produce 167 kg of methane so the claim that it can product 134 kg is valid.
To drive the reaction forward would require an increase in the temperature to a value large enough
so that T∆S was greater than ∆H .
∆G = ∆H − T ∆S T = (∆G − ∆H)/∆S
494
Chapter 19
The overall assessment is that this project is not one in which you should not invest the funds.
19.122 The equilibrium constant can be used to determine ∆Go and the reaction data can be used to determine the
enthalpy of the neutralization reaction. Then we need to see how these two results can be used along with
our knowledge of equilibrium and thermodynamic relationships to calculate the entropy of the reaction.
∆Go = − RT lnK =RT pK = 8.314 J mol−1 K−1 x 298 K x 5.83 = 1.44 x 104 J or 14.4 kJ mol−1
The neutralization reaction is a 1:1 mole ratio. Also, you have two different volumes at two different initial
temperatures. Finally, you have an excess of on reactant so this is a limiting reagent problem.
Therefore, 0.289 mmol of acid react and the heat of reaction will be for this many mmoles reacting.
qrxn = mCP∆T
= 100.0 g x 4.184 J g−1 oC−1 x (21.26 – 24.88) oC + 45.6 g x 4.184 J g−1 oC−1 x (22.18 – 24.88) oC
= -2029 J
This is the amount of heat released when 0.289 mmol of acid react. Therefore, the molar enthalpy of the
reaction is:
-2029 J/(0.289 mmol x 1 mol/1000 mmol) = −7.02 x 106 J mol−1 or -702 kJ mol−1
To summarize,
HA A− + H+ ∆G o = 14.4 kJ mol−1
HA + OH− → A− + H2O ∆Ho = −702 kJ mol−1
Using Hess’s Law we can add together a series of reactions and their enthalpies to achieve the desired
equilibrium reaction and its enthalpy.
∆Ho = 1 mol OH− x (-230.0 kJ mol−1) − 1 mol H2O x (-285.9 kJ mol−1) = 55.9 kJ
∆So = {14.4 kJ – (-702 kJ)}/298 K = 2.40 kJ mol−1 K−1 or 2.4 x 103 J mol−1 K−1
495