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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.)

∆E = –P∆V

but ∆V is negative for a compression so ∆E increases and T increases.

Energy is added to the system in the form of work.

∆H = {4 mol NO2(g) × (34 kJ/mol)} – {2 mol N2O × (81.5 kJ/mol) + 3 mol O2 × (0 kJ/mol)}

∆H = –27 kJ

∆E – ∆H = –2.64 kJ

∆E is more exothermic.

= –217.1 kJ + 2.48 kJ

= –214.6 kJ

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

∆Sof = (1 mol NH 3 ) × − mol N 2 × + mol H 2 ×

mol K 2 mol K 2 mol K

∆Sof = –99.1 J K–1

∆S° = {1 mol × (69.96 J mol–1 K–1) + 1 mol × (114 J mol–1 K–1)}

– {1 mol × (40 J mol–1 K–1) + 2 mol × (186.7 J mol–1 K–1)}

∆S° = –229 J/K

∆S° = {1 mol × (229.5 J mol–1 K–1)}

– {1 mol × (130.6 J mol–1 K–1) + 1 mol × (219.8 J mol–1 K–1)}

∆S° = –120.9 J/K

∆H oN2 O4 (g) = 9.67 kJ mol–1

∆SoN2 O4 (g) = (1 mol N2O4)(304 J mol–1 K–1) – (1 mol N2)(191.5 J mol–1 K–1) –

(2 mol O2)(205.0 J mol–1 K–1) = –297.5 J K–1

∆G = ∆H – T ∆Sof

o

f

o

f

∆G of = 98.3 kJ mol–1

∆S° = {2 mol × (90.0 J mol–1 K–1)}

– {3 mol × (205.0 J mol–1 K–1) + 4 mol × (27 J mol–1 K–1)}

∆S° = –543 J/K = –0.543 kJ/mol

∆H° = {2∆Hf°[Fe2O3(s)]} – {3∆Hf°[O2(g)] + 4∆Hf°[Fe(s)]}

∆H° = {2 mol × (–822.2 kJ/mol)} – {3 mol × (0.0 kJ/mol) + 4 × (0.0 kJ/mol)}

∆H° = –1644 kJ

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

∆Go = {2 mol Fe(s) × ∆Gf°[Fe(s)] + 3 mol CO2(g) × ∆Gf°[CO2(g)]}

– {1 mol Fe2O3(s) × ∆Gf°[Fe2O3(s)] + 3 mol CO(g) × ∆Gf°[CO(g)]}

∆Go = {2 mol Fe(s) × 0 kJ mol–1 + 3 mol CO2(g) × –394.4 kJ mol–1}

– {1 mol Fe2O3(s) × –741.0 kJ mol–1 + 3 mol CO(g) × –137.3 kJ mol–1}

∆Go = –30.3 kJ

466

Chapter 19

∆G°rxn = {2 mol × (+51.84 kJ mol–1)}

– {2 mol × (+86.69 kJ mol–1) + 1 mol × (0 kJ mol–1)}

∆G°rxn = –69.7 kJ/mol

∆G°rxn = {1 mol × (–750.2 kJ mol–1) + 2 mol × (–228.6 kJ mol–1)}

– {1 mol × (–896.76 kJ mol–1) + 2 mol × (–95.27 kJ mol–1)}

∆G°rxn = –120.1 kJ/mol

∆G°rxn = {2∆Gf°[CO2(g)] + 3∆Gf°[H2O(l)]} – {∆Gf°[C2H5OH(l)] + 3∆Gf°[O2(g)]}

∆G°rxn = {2 mol × (–394.4 kJ mol–1) + 3 mol × (–237.2 kJ mol–1)} – {1 mol × (–174.8 kJ mol–1)

+ 3 mol × (0 kJ mol–1)}

G°rxn = –1325.6 kJ

For 125 g C2H5OH:

1 mol C 2 H 5 OH

mol C2H5OH = 125 g C2H5OH = 2.71 mol C2H5OH

46.08 g C 2 H 5 OH

Maximum work:

(1325.6 kJ mol–1)(2.71 mol C2H5OH) = 3596 kJ

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)

∆G° = 2∆Gf°[Al2O3(s)] – {3∆Gf°[O2(g)] + 4∆Gf°[Al(s)]}

∆G° = 2 mol × (–1576.4 kJ/mol) – {3 mol × (0.0 kJ/mol) + 4 mol × (0.0 kJ/mol)}

∆G° = –3152.8 kJ, for the reaction as written.

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:

∆S° = S°[Hg(g)] – S°[Hg(l)]

∆S° = (175 × 10–3 kJ mol–1 K–1) – (76.1 × 10–3 kJ mol–1 K–1)

∆S° = 98.9 × 10–3 kJ mol–1 K–1

1

∆G° = ∆Gf°[SO3(g)] – {∆Gf°[SO2(g)] + ∆Gf°[ O2(g)]}

2

1

∆G° = 1 mol × (–370.4 kJ/mol) – {1 mol × (–300.4 kJ/mol) + (0.0 kJ/mol)}

2

∆G° = –70.0 kJ/mol

∆G° = {2∆Gf°[HCl(g)] + ∆Gf°[CaCO3(s)]}

– {∆Gf°[CaCl2(s)] + ∆Gf°[H2O(g)] + ∆Gf°[CO2(g)]}

∆G° = {2 mol × (–95.27 kJ/mol) + 1 mol × (–1128.8 kJ/mol)}

– {1 mol × (–750.2 kJ/mol) + 1 mol × (–228.6 kJ/mol) +

1 mol × (–394.4 kJ/mol)}

∆G° = +53.9 kJ

∆G° is positive, the reaction is not spontaneous, and we do not expect to see products formed from

reactants.

∆G° = 119.2 kJ – (348 K)(0.3548 kJ/K)

–4.3 kJ

468

Chapter 19

– {2∆Gf°[NaHCO3(s)]}

∆G° = {1 mol × (–1048 kJ/mol) + 1 mol × (–394.4 kJ/mol) + 1 mol × (–228.6 kJ/mol)}

– {2 mol × (–851.9 kJ/mol)}

∆G° = +32.8 kJ

– {2∆Hf°[NaHCO3(s)]}

∆H° = {1 mol × (–1131 kJ/mol) + 1 mol × (–393.5 kJ/mol) + 1 mol × (–241.8 kJ/mol)}

– {2 mol × (–947.7 kJ/mol)}

∆H° = +129.1 kJ

– {2Sf°[NaHCO3(s)]}

∆S° = {1 mol × (136 J/mol K) + 1 mol × (213.6 J/mol K) + 1 mol × (188.7 J/mol K)}

– {2 mol × (102 J/mol K)}

∆S° = +334.3 J K–1 = 0.3343 kJ K–1

∆G o490 = 129.1 kJ – (490 K)(0.3343 kJ K–1) = –34.7 kJ

The equilibrium shifts to products.

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.

∆G° = –(8.314 J K–1 mol–1)(25 + 273 K) × ln(6.9 × 105) = –33 × 103 J

∆G° = –33 kJ

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.

Thus, P in pascals times ∆V in m3 is: N/m2 × m3 = N · m

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.

(d) negative (e) negative (f) positive

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

P = 30.0 lb/in2 × 1 atm/14.7 lb/in2 = 2.04 atm

24.0 in3 × (2.54 cm/in)3 × 1 L/1000 cm3 = 0.393 L

0.802 L·atm × 101.3 J/L·atm = 81 J

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

W = –P∆V = –(1.00 atm)(24.5 L) = –24.5 L atm

475

Chapter 19

∆H° = { ∆Hof [Pb(s)] + ∆Hof [N2(g)] + 3 ∆Hof [H2O(g)]}

– {3 ∆Hof [PbO(s)] + 2 ∆Hof NH3(g)]}

∆H° = {3 mol × (0 kJ/mol) + 1 mol × (0 kJ/mol) + 3 mol × (–241.8 kJ/mol)}

– {3 mol × (–219.2 kJ/mol) + 2 mol × (–46.19 kJ/mol)}

∆H° = + 24.58 kJ

∆E = ∆H° – ∆nRT

∆E = 24.58 kJ – (+2 mol)(8.314 J/mol K)(10–3 kJ/J)(298 K) = 19.6 kJ

∆H° = { ∆Hof [NaCl(s)] + ∆Hf [H2O(l)]} – { ∆Hof [NaOH(s)] + ∆Hof [HCl(g)]}

∆H° = {1 mol × (–411.0 kJ/mol) + 1 mol × (–285.9 kJ/mol)}

– {1 mol × (–426.8 kJ/mol) + 1 mol × (–92.3)}

∆H° = –178 kJ

∆E = ∆H° – ∆nRT

∆E = –178 kJ – (–1)(8.314 J/mol K)(10–3 kJ/J)(298 K) = –175 kJ

∆H° = { ∆Hof [Fe2O3(s)] + 2 ∆Hof [Al(s)]} – { ∆Hof [ Al2O3(s)] + 2 ∆Hof [Fe(s)]}

∆H° = {1 mol × (–822.2 kJ/mol) + 2 mol ×(0 kJ/mol)}

– {1 mol × (–1669.8 kJ/mol) + 2 mol × (0 kJ/mol)}

∆H° = 847.6 kJ

∆H° = { ∆Hof [C2H6(g)] + ∆Hof [H2(g)]} – {2 ∆Hof [CH4(g)]}

∆H° = {1 mol × (–84.667 kJ/mol) + 1 mol × (0.0 kJ/mol)}

– {2 mol × (–74.848 kJ/mol)}

∆H° = 65.029 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

∆E = –2509 kJ

(b) C2H2(g) + 5N2O(g) 5N2(g) + H2O(g) + 2CO2(g)

∆H° = {5 ∆Hof [N2(g)] + ∆Hof [H2O(g)] + 2 ∆Hof [CO2(g)]}

– {5 ∆Hof [N2O(g)] + ∆Hof [C2H2(g)]}

∆H° = {5 mol × (0.0 kJ/mol) + 1 mol × (–241.8 kJ/mol) + 2 mol × (–393.5 kJ/mol)}

– {5 mol × (81.57 kJ/mol) + 1 mol × (226.75 kJ/mol)}

∆H° = –1663.4 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

∆H° = { ∆Hof [HCl(g)] + ∆Hof [NH3(g)]} – { ∆Hof [NH4Cl(s)]}

∆H° = {1 mol × (–92.3 kJ/mol) + 1 mol × (–46.19 kJ/mol)}

– {1 mol × (–315.4 kJ/mol)}

∆H° = 176.9 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

∆H° = {3 ∆Hof [CO2(g)] + 3 ∆Hof [H2O(g)]} – { ∆Hof [(CH3)2CO(l)] + 4 ∆Hof [O2(g)]}

∆H° = {3 mol × (–393.5 kJ/mol) + 3 mol × (–241.8 kJ/mol)}

– {1 mol × (–248.1 kJ/mol) + 4 × (0 kJ/mol)}

∆H° = –1657.8 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

−167.17 kJ

Amount of Energy at 212 °C = 4.43 mol N2O = –370 kJ

2 mol N 2 O

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.

∆H° = {1 mol × (–84.5 kJ/mol)} – {1 mol × (226.75 kJ/mol) + 2 mol × (0.0 kJ/mol)}

∆H° = –311 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.

∆H° = {1 mol × (–92.3 kJ/mol) + 1 mol × (–46.19 kJ/mol)} – {1 mol × (–315.4 kJ/mol)}

∆H° = 176.9 kJ ∴ not favorable from the standpoint of enthalpy.

(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.

– {5 ∆Hof [N2O(g)] + ∆Hof [C2H2(g)]}

∆H° = {5 mol × (0.0 kJ/mol) + 1 mol × (–241.8 kJ/mol)

+ 2 mol × (–393.5 kJ/mol)} – {5 mol × (81.57 kJ/mol)

478

Chapter 19

∆H° = –1663 kJ ∴ favorable from the standpoint of enthalpy.

The factors needed to be consider in order to determine the sign of ∆S are

(1) the number of moles of products versus reactants

in this case the number of moles increases

(2) the state of the products versus reactants

both products and reactants are gases

(3) the complexity of the molecules

N2O is more complex than either N2 or O2

∆S is expected to be positive.

The factors needed to be consider in order to determine the sign of ∆S are

(1) the number of moles of products versus reactants

in this case the number of moles are the same

(2) the state of the products versus reactants

both products and reactants are gases

(3) the complexity of the molecules

HI is more complex than either H2 or I2

∆S is expected to be negative.

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.

∆S° = {2 mol × (192.5 J mol–1 K–1)} – {3 mol × (130.6 J mol–1 K–1)

+ 1 mol × (191.5 J mol–1 K–1)}

∆S° = –198.3 J/K ∴ not spontaneous from the standpoint of entropy.

∆S° = {1 mol × (126.8 J mol–1 K–1)}

– {2 mol × (130.6 J mol–1 K–1) + 1 mol × (197.9 J mol–1 K–1)}

∆S° = –332.3 J/K ∴ not favored from the standpoint of entropy alone.

∆S° = {6 mol × (188.7 J mol–1 K–1) + 4 mol × (213.6 J mol–1 K–1)}

– {7 mol × (205.0 J mol–1 K–1) + 2 mol × (229.5 J mol–1 K–1)}

∆S° = +92.6 J/K ∴ favorable from the standpoint of entropy alone.

– {S°[H2SO4(l)] + S°[Ca(OH)2(s)]}

479

Chapter 19

– {1 mol × (157 J mol–1 K–1) + 1 mol × (76.1 J mol–1 K–1)}

∆S° = +14 J/K ∴ favorable from the standpoint of entropy alone.

∆S° = {2 mol × (191.5 J mol–1 K–1) + 1 mol × (248 J mol–1 K–1)}

– {2 mol × (220.0 J mol–1 K–1) + 1 mol × (31.9 J mol–1 K–1)}

∆S° = +159 J/K ∴ favorable from the standpoint of entropy alone.

∆S° = {1 mol × (96.2 J mol–1 K–1)}

– {1/2 mol × (223.0 J mol–1 K–1) + 1 mol × (42.55 J mol–1 K–1)}

∆S° = –57.9 J/K

∆S° = {1 mol × (188.7 J mol–1 K–1)}

– {1/2 mol × (205.0 J mol–1 K–1) + 1 mol × (130.6 J mol–1 K–1)}

∆S° = –44.4 J/K

∆S° = {1 mol × (69.96 J mol–1 K–1)}

– {1/2 mol × (205.0 J mol–1 K–1) + 1 mol × (130.6 J mol–1 K–1)}

∆S° = –163.1 J/K

– {S°[CaCO3(s)] + S°[H2SO4(l)]}

∆S° = {1 mol × (213.6 J mol–1 K–1) + 1 mol × (188.7 J mol–1 K–1)

+ 1 mol × (107 J mol–1 K–1)} – {1 mol × (92.9 J mol–1 K–1)

+ 1 mol × (157 J mol–1 K–1)}

∆S° = +259 J/K

∆S° = {1 mol × (94.6 J mol–1 K–1)}

– {1 mol × (186.7 J mol–1 K–1) + 1 mol × (192.5 J mol–1 K–1)}

∆S° = –284.6 J/K

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.

5.69 130.6 229.5

∆S° = 229.5 – [2(5.69) + 3(130.6)]

229.5 – 11.38 – 391.8

=– 173.7 J/K.mol

5.69 205.0 130.6 200.4

∆S° = 200.4 – [3(5.69) + ½ (205.0) + 3 (130.6)]

200.4 – 17.07 – 102.5 = 391.8

480

Chapter 19

= –311.0 J/K.mol

33.15 31.9 205.0 130.6 300.4

∆S° = 300.4 – [1(33.15) + 1(31.9) + 9 2 (205.0) +5(130.6)]

300.4 – 33.15 –31.9 – 922.5 – 653.0

∆S° = –1340.2 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.

51.0 205.0 130.6 64.18

∆S° = 64.18 – [51.0 + (½)(205.0) + (½) 130.6]

64.18 – 51.0 – 102.5 – 65.3

∆S° = – 154.62 J/K.mol

27 205.0 90.0

∆S° = 90.0 – [(2)(27) + ( 3 2 ) (205)]

90.0 – 54 – 307.5

∆S° = –271.5 J/K.mol

42.55 191.5 205.0 141.0

∆S° = 141.0 – [42.55 + (½)(191.5) + ( 3 2 )(205.0)]

= 141.0 – 42.55 – 95.8 – 307.5

∆S° = – 304.85 J/K.mol

∆S° = {2S°[HNO3(l)] + S°[NO(g)]} – {3S°[NO2(g)] + S°[H2O(l)]}

∆S° = {2 mol × (155.6 J mol–1 K–1) + 1 mol × (210.6 J mol–1 K–1)}

– {3 mol × (240.5 J mol–1 K–1) + 1 mol × (69.96 J mol–1 K–1)}

∆S° = –269.7 J/K

19.65 ∆S° = (sum S°[products]) – (sum S°[reactants])

∆S° = {S°[HC2H3O2(l)] + S°[H2O(l)]} – {S°[C2H5OH(l)] + S°[O2(g)]}

∆S° = {1 mol × (160 J mol–1 K–1) + 1 mol × (69.96 J mol–1 K–1)}

– {1 mol × (161 J mol–1 K–1) + 1 mol × (205.0 J mol–1 K–1)}

∆S° = –136 J/K

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

+ 1/2 mol × (205.0 J mol–1 K–1) + 1 mol × (223.0 J mol–1 K–1)}

o

∆Sf = –47 J mol–1 K–1 or –47 J/K

= –209 kJ/mol

2Al(s) + 3/2O2(g) Al2O3(s)

∆Sof = {S°[Al2O3(s)]} – {2S°[Al(s)] + 3/2S°[O2(g)]}

∆Sof = {1 mol × (51.0 J mol–1 K–1)} – {2 mol × (28.3 J mol–1 K–1)

+ 3/2 mol × (205.0 J mol–1 K–1)}

∆Sof = –313.1 J/K or –313.1 J mol–1 K–1 = –0.3131 kJ mol–1 K–1

∆G f = –1576.5 kJ/mol

This value agrees well with the value listed in Appendix C2.

∆G° = {1 mol × (–689.9 kJ/mol)} –

{1 mol × (–237.2 kJ/mol) + 1 mol × (–370 kJ/mol)}

∆G° = –82.3 kJ

– { ∆G of [CaO(s)] + 2 ∆G of [NH4Cl(s)]}

∆G° = {2 mol × (–16.7 kJ/mol) + 1 mol × (–237.2 kJ/mol)

+ 1 mol × (–750.2 kJ/mol)} – {1 mol × (–604.2 kJ/mol)

+ 2 mol × (–203.9 kJ/mol)}

∆G° = –8.8 kJ

∆G° = {1 mol × (–689.9 kJ/mol) + 1 mol × (–750.2 kJ/mol)}

– {1 mol × (–1320.3 kJ/mol) + 2 mol × (–95.27 kJ/mol)}

∆G° = +70.7 kJ

∆G° = {1 mol × (–228.6 kJ/mol) + 1 mol × (–750.2 kJ/mol)}

– {2 mol × (–95.27 kJ/mol) + 1 mol × (–604.2 kJ/mol)}

∆G° = –184.1 kJ

482

Chapter 19

∆G° = {2 mol × (0.0 kJ/mol) + 1 mol × (–750.2 kJ/mol)}

– {2 mol × (–109.7 kJ/mol) + 1 mol × (0.0 kJ/mol)}

∆G° = –530.8 kJ

∆G° = {1 mol × (86.69 kJ/mol) + 2 mol × (–79.91 kJ/mol)}

– {3 mol × (51.84 kJ/mol) + 1 mol × (–237.2 kJ/mol)}

∆G° = +8.6 kJ

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:

2NO(g) + O2(g) 2NO2(g), ∆G° = -69.70 kJ (2)

19.71 Add the reverse of the first equation to the second equation plus twice the third equation:

COCl2(g) + H2O(l) CO2(g) + 2HCl(g), ∆G° = –141.8 kJ

2NH3(g) + 2HCl(g) 2NH4Cl(s), ∆G° = –183.9 kJ

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:

∆G° = {3 ∆G of [H2O(g)] + 2 ∆G of [CO2(g)]} – {3 ∆G of [O2(g)] + ∆G of [C2H5OH(l)]}

∆G° = {3 mol × (–228.6 kJ/mol) + 2 mol × (–394.4 kJ/mol)}

– {3 mol × (0.0 kJ/mol) + 1 mol × (–174.8 kJ/mol)}

∆G° = –1299.8 Kj

Since this is for 2 mols C2H5OH we must multiply the ∆G° value by 2.

–1299.8 kJ (2) = –2599.6 kJ

CH4(g) + 2O2(g) CO2(g) + 2H2O(g)

∆G° = { ∆G of [CO2(g)] + 2 ∆G of [H2O(g)]} – { ∆G of [CH4(g)] + 2 ∆G of [O2(g)]}

∆G° = {1 mol × (–394.4 kJ/mol) + 2 mol × (–228.6 kJ/mol)}

– {1 mol × (–50.79 kJ/mol) + 2 mol × (0.0 kJ/mol)}

∆G° = –800.8 kJ/mol

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

Teq = ∆H/∆S, and assuming that ∆S and ∆H are independent of temperature, we have:

Teq = (10.0 × 103 J mol–1) ÷ (9.50 J mol–1 K–1) = 1.05 × 103 K or 780 °C

Thus ∆H = T∆S, and if we assume that both ∆H and ∆S are independent of temperature, we have:

∆S = 101 J mol–1 K–1

∆S = 96.9 J mol–1 K–1

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.

∆G° = {3 ∆G of [Pb(s)] + ∆G of [N2(g)] + 3 ∆G of [H2O(g)]}

– {3 ∆G of [PbO(s)] + 2 ∆G of [NH3(g)]}

∆G° = {3 mol × (0.0 kJ/mol) + 1 mol × (0.0 kJ/mol)

+ 3 mol × (–228.6 kJ/mol)} – {3 mol × (–189.3 kJ/mol)

+ 2 mol × (–16.7 kJ/mol)}

∆G° = –84.5 kJ ∴ the reaction is spontaneous.

∆G° = { ∆G f [NaCl(s)] + ∆G f [H2O(l)]} – { ∆G f [NaOH(s)]+ ∆G f [HCl(g)]}

∆G° = {1 mol × (–384.0 kJ/mol) + 1 mol × (–237.2 kJ/mol)}

– {1 mol × (–382 kJ/mol) + 1 mol × (–95.27)}

∆G° = –144 kJ ∴ the reaction is spontaneous.

484

Chapter 19

∆G° = { ∆G of [Fe2O3(s)] + 2 ∆G of [Al(s)]} – { ∆G of [Al2O3(s)] + 2 ∆G of [Fe(s)]}

∆G° = {1 mol × (–741.0 kJ/mol) + 2 mol × (0.0 kJ/mol)}

– {1 mol × (–1576.4 kJ/mol) + 2 mol × (0.0 kJ/mol)}

∆G° = +835.4 k ∴ the reaction is not spontaneous.

∆G° = { ∆G of [C2H6(g)] + ∆G of [H2(g)]} – {2 ∆G of [CH4(g)]}

∆G° = {1 mol × (–32.9 kJ/mol) + 1 mol × (0.0 kJ/mol)}

– {2 mol × (–50.79 kJ/mol)}

∆G° = +68.7 kJ ∴ the reaction is not spontaneous.

1

19.80 PCl3(g) + O 2( g ) → POCl3(g)

2

∆G° = {1 mol × (–512.9kJ/mol)}

– {1 mol × (–267.8 kJ/mol) + 1/2 mol × (0 kJ/mol)}

∆G° = –245.1 kJ = –2.45 × 105 J

–2.45 × 105 J = –RTlnKp = –(8.314 J/K mol)(298 K) × lnKp

lnKp = 98.9 and Kp = 9.20 x 1042

∆G° = {1 mol × (–300.4 kJ/mol) + 1 mol × (0 kJ/mol)} – {1 mol × (–370.4 kJ/mol)}

∆G° = 70 kJ = 7. 0 × 104 J

7.0 × 104 J = –RTlnKp = –(8.314 J/K mol)(298 K) × lnKp

lnKp = 28.25 and Kp = 5.37 × 10–13

– {1 × ∆G f [N2H4(g)] + 2 × ∆G f [O2(g)]}

∆G° = {2 mol × (86.69 kJ/mol) + 2 mol × (–228.6 kJ/mol)}

– {1 mol × (159.3 kJ/mol) + 2 mol × (0.0 kJ/mol)}

∆G° = – 443.1 kJ = – 4.431 × 105 J

− 4.431× 105 J = –RTlnKp = –(8.314 J/K mol)(298 K) × lnKp

lnKp = 178.8 and Kp = 4.728 × 1077

(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

–9.67 × 103 J = –(8.314 J/K mol)(1273 K) × ln Kp

ln Kp = 0.914 ∴ Kp = 2.49

N 2 O

NO 2 [ NO ] ( 0.200)( 0.40)

Since the value of Q is less than the value of K, the system is not at equilibrium and must shift to the right

to reach equilibrium.

ln Kp = –14.3 ∴ Kp = 6.40 × 10–7

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.

–50.79 × 103 J = –(8.314 J K–1 mol–1)(298 K) × ln Kp

ln Kp = 20.50

Taking the exponential of both sides of this equation gives: Kp = 8.000 × 108

This is a favorable reaction, since the equilibrium lies far to the side favoring products and is worth

studying as a method for methane production.

∆G°T = –RT ln Kc

–33 × 103 J = –(8.314 J K–1 mol–1)(310 K) × ln Kc

ln Kc = 13

Kc = 3.6 × 105

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.

∆G°500 = –(8.314 J K–1 mol–1)(500 K) ln (6.25 × 10–3)

∆G°500 = 2.11 × 104 J = 21.1 kJ

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

–235.3 = 2989.85 + x

x = –3225.2 kJ

∆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

∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)

∆Hf [CS2(g)] = 115.3 kJ/mol = [716.67 + 2 × 276.98] – [2 × C=S]

The C=S double bond energy is therefore given by the equation:

C=S = –(115.3 – 716.67 – 2 × 276.98) ÷ 2 = 577.7 kJ/mol

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

∆Hf = sum( ∆Hf [gaseous atoms]) – sum(average bond energies in the molecule)

∆Hf [SF6(g)] = –1096 kJ/mol = [277.0 + 6 × 79.14] – [6 × S—F]

S—F = (1096 + 277.0 + 6 × 79.14) ÷ 6 = 308.0 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)

= 85 kJ/mol

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

Substituting the given information: P × ∆V = 101,325 Pa × 1 dm3

Now it is true that 1 dm = 0.1 m, so: 1 dm3 = (0.1 m)3 = 1 × 10–3 m3

Also, 1 Pa = 1 N/m2

Thus we have: P(Pa) × ∆V(dm3) = (101,325 N/m2)(1 × 10–3 m3) = 101.325 N·m

101.325 N·m × 1 J/1 N·m = 101.325 J

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

w= –P∆V = (–2.0 atm)(30 L – 12 L) = –36 L atm

If the temperature is constant, then heat must be absorbed to balance the amount of energy expended as

work and the amount of heat absorbed must be equal to the amount of work expended.

q = 36 L atm

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

w1 = –(2 atm)(10.0 L – 5.00 L) = –10.0 L atm.

The work performed during the second stage of expansion is:

w2 = –(1 atm)(20.0 L – 10.0 L) = –10.0 L atm.

The sum for the whole stepwise process is w1 + w2 = –20.0 L atm. Thus, we see that more work is

performed in this multi–step expansion than in a single expansion. To obtain more work, the expansion

needs to be done in smaller steps

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.

(b) H2(g) + 2C(s) + 2O2(g) H2C2O4(s) ∆Hf = ? kJ mol–1

( c) ∆H°comb = { ∆Hof (H2O(l)) + 2 ∆Hof (CO2(g))} – { ∆Hof (H2C2O4(s)) + 1/2 ∆Hof (O2(g))}

Rearranging;

∆Hf (H2C2O4(s)) = { ∆Hof (H2O(l)) + 2 ∆Hof (CO2(g))}

–∆H°comb

= –285.8 kJ + 2(–393.5 kJ) – (–246.05 kJ) = –826.8 kJ

(d) ∆Sf = S°(H2C2O4(s)) – {Sf°(H2(g)) + 2S°(C(g))+ 2S°(O2(g))}

= 120.1 J/K – {130.6J/K + 2(5.69 J/K) + 2(205.0 J/K)}

= –431.9J/mol K

∆S°comb = {S°(H2O(l)) + 2S°(CO2(g))} – {S°(H2C2O4(g)) + 1/2S°(O2(g))}

= {69.96 J/K + 2(213.6 J/K)} – {120.1 J/K + 1/2(205.0 J/K) = 274.6 J/mol K

(e) ∆G f = ∆Hf – T ∆Sf

= –826.8 kJ – (298 K)(–0.4319 kJ/K) = –698.1 kJ

∆Gcomb° = ∆Hcomb° – T∆Scomb°

= –246.05 kJ – (298K)(0.2746 kJ/K) = –327.9 kJ

ATP + H2O ADP + phosphate ∆G = –32.22 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.

∆G = {8 × ∆G of [CO 2 (g)] + 10 × ∆G fo [H 2 O(g)]}

− {2 × ∆G of [C4 H10 (g)] + 13 × ∆G of [O 2 (g)]}

∆G of [C4 H10 (g)] =1/2[ {8 × ∆G of [CO 2 (g)] + 10 × ∆G fo [H 2 O(g)]}

− {13 × ∆G of [O 2 (g)]} − ∆G ]

1

∆G of [C 4 H10 (g)] =

[{(8 mol × –394.4 kJ mol–1) + (10 mol × –228.6 kJ mol–1)} – (13 mol × 0 kJ mol–1) –

2

(–5407 kJ)] = –17 kJ

∆G° = –RTlnK

–17,000 J = –(8.314 J mol–1 K–1)(298 K)lnK

ln K = 6.86

Kc = 954

∆G1173

o

= –RTlnK

∆G1173

o

= –(8.314 J mol–1 K–1)(1773 K)(ln 5.67)

490

Chapter 19

∆G1173

o

= –25,600 J = –25.6 kJ

N2(g) + 3O2(g) + H2(g) 2HNO3(l) ∆G° = –159.82 kJ

H2O(l) H2(g) + 1/2O2(g) ∆G° = 237.2 kJ

I 1.00 – –

C –2x +x +2x

E 1.00 – 2x +x +2x

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

∆G = ∆H – T∆S

∆G = –42.9 kJ – (773 K)(–0.0261 kJ K–1) = –22.7 kJ

∆G o773 = –RTlnK

–22,700 J = –(8.314 J mol–1)(773 K)lnK

ln K = 3.53

K = 34.2

I 0.06 0.06 – –

C –x –x +x +x

E 0.06 –x 0.06 – x +x +x

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

↓(1) ↓(2) ↑(4)

C(g) + 4Cl(g) CCl4(g)

(3)

Step 1: ∆H = 717 kJ

Step 2: ∆H = 4(121.5 kJ) = 486 kJ

Step 3: ∆Hf°(CCl4(g)) = 4(BE(C–Cl)) = 4(338 kJ) = –1352 kJ

Step 4: ∆Hcond = –29.9 kJ

I 0.157 0.0968 –

C –2x –3x +4x

E 0.157 –2x 0.0968 – 3x 4x

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

(1) (2) (3)

(2) ∆H o2 = ∆H of O(g) = 2 mol × 249.17 kJ mol–1 = 498.34 kJ

492

Chapter 19

The sum of the three steps is the total energy input: 933.6 kJ

The sum of the bond energies for SF2O2(g) less the total energy input to form the gaseous atoms is the

enthalpy of formation.

The sum of the bond energies:

2 S―F 2 mol × 308.0 kJ/mol = 616 kJ

2 S═O 2 mol × x kJ/mol = 2x kJ

∆H of SF2 O2 (g) = 933.6 kJ + [–616 kJ + 2x kJ]

–858 kJ = 317 kJ + 2x kJ

x = –588 kJ

The bond energy for S═O is 588 kJ

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.

HC3H5O2(aq) + OH−(aq) → −

C3H5O2 (aq) + H2O ∆Ho = -49.23 kJ mol−1

The entropy change for the reaction can be determined from the enthalpy of the reaction and the

equilibrium constant for propionic acid.

= {− 8.314 J mol−1 K−1 x 298 K x ln (1.3 x 10−5) – 6,663 J mol−1}/298 K

= 71.2 J mol−1 K−1

493

Chapter 19

(1) Does a catalyst shift equilibrium?

(2) Is the mass of product consistent with the mass of methane in 117 m3 at STP?

(3) Does thermodynamics favor the products?

(4) Is the equilibrium constant large or small?

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

5220 mol CH 4 x x = 1.67 x 105 mol CH3 OH

mol CH 4 mol CH3OH

The reaction should produce 167 kg of methane so the claim that it can product 134 kg is valid.

= 1 mol CH3OH x(−166.2 kJ mol−1) –{1 mol H2O x (-237.2 kJ mol−1) + 1 mol CH4 x (-50.79 kJ mol−1)

= 121.8 kJ

–{1 mol H2O x 69.96 J mol−1 K−1 ) + 1 mol CH4 x (186.2 J mol−1 K−1)

= 1.24 J K−1

Entropy favors the reaction, but only slightly. Therefore, the enthalpy is large and positive.

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

∆G = − RT ln K

121.8 kJ x 1000 J kJ−1 = −8.314 J K−1 mol−1 x 298 K ln K

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.

mmol of base = 45.6 mL x 0.00634 M = 0.289 mmol

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

H2O H+(aq) + OH−(aq) ∆Ho = 55.9 kJ mol−1

HA A− + H+ ∆Ho = −646.1 kJ mol−1

∆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

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