Chapter 6: Thermochemistry 25°C:

Example 6.1
A certain gas expands in volume from 2.0 L to 6.0 L
at constant temperature. Calculate the work done by Ans: From the chemical equation we see that 3 moles
the gas if it expands (a) against a vacuum and (b) of gases are converted to 2 moles of gases so that
against a constant pressure of 1.2 atm.

Ans: (a) Because the external pressure is zero, no Using 8.314 J/K •mol for R and T = 298 K in
work is done in the expansion. Equation (6.10), we write

(b) The external, opposing pressure is 1.2 atm, so

Example 6.5
A 466-g sample of water is heated from 8.50°C to
To convert the answer to joules, we write 74.60°C. Calculate the amount of heat absorbed (in
kilojoules) by the water.

Ans:

Example 6.2
The work done when a gas is compressed in a
cylinder like that shown in Figure 6.5 is 462 J.
During this process, there is a heat transfer of 128 J
from the gas to the surroundings. Calculate the
energy change for this process. Example 6.6
A quantity of 1.435 g of naphthalene (C10H8), a
Ans: To calculate the energy change of the gas, we pungent-smelling substance used in moth repellents,
need Equation (6.1). Work of compression is positive was burned in a constant-volume bomb calorimeter.
and because heat is released by the gas, q is negative. Consequently, the temperature of the water rose from
Therefore, we have 20.28°C to 25.95°C. If the heat capacity of the bomb
plus water was 10.17 kJ/°C, calculate the heat of
combustion of naphthalene on a molar basis; that is,
find the molar heat of combustion.

As a result, the energy of the gas increases by 334 J. Ans: The heat absorbed by the bomb and water is
equal to the product of the heat capacity and the
Example 6.3 temperature change. From Equation (6.16), assuming
Given the thermochemical equation no heat is lost to the surroundings, we write

Ans: We need to fi rst calculate the number of moles

of SO2 in 87.9 g of the compound and then find the Because qsys = qcal + qrxn = 0, qcal = -qrxn. The
number of kilojoules produced from the exothermic heat change of the reaction is -57.66 kJ. This is the
reaction. The enthalpy change for this reaction is heat released by the combustion of 1.435 g of C 10H8;
given by therefore, we can write the conversion factor as

and the heat released to the surroundings is 136 kJ. The molar mass of naphthalene is 128.2 g, so the heat
of combustion of 1 mole of naphthalene is
Example 6.4
Calculate the change in internal energy when 2 moles
of CO are converted to 2 moles of CO2 at 1 atm and
Example 6.7 Energy Changes in Chemical Reactions
A lead (Pb) pellet having a mass of 26.47 g at Review Questions
89.98°C was placed in a constant-pressure 6.7 Define these terms: thermochemistry, exothermic
calorimeter of negligible heat capacity containing process, endothermic process.
100.0 mL of water. The water temperature rose from 6.° Stoichiometry is based on the law of conservation
22.50°C to 23.17°C. What is the specific heat of the of mass. On what law is thermochemistry based?
lead pellet? 6.9 Describe two exothermic processes and two
endothermic processes.
Ans: Treating the calorimeter as an isolated system 6.10 Decomposition reactions are usually
(no heat lost to the surroundings), we write endothermic, whereas combination reactions are
usually exothermic. Give a qualitative explanation for
these trends.

The heat gained by the water is given by First Law of Thermodynamics

Review Questions
6.11 On what law is the first law of thermodynamic
-based? Explain the sign conventions in the equation
Because the heat lost by the lead pellet is equal to the ΔU = q + w.
heat gained by the water, qPb = -280.3 J. Solving for 6.12 Explain what is meant by a state function. Give
the specific heat of Pb, we write two examples of quantities that are state functions
and two that are not.
6.13 The internal energy of an ideal gas depends only
on its temperature. Do a first-law analysis of this
process. A sample of an ideal gas is allowed to
expand at constant temperature against atmospheric
pressure. (a) Does the gas do work on its
surroundings? (b) Is there heat exchange between the
Questions and Problems system and the surroundings? If so, in which
direction? (c) What is ΔU for the gas for this process?
Definitions 6.14 Consider these changes.
Review Questions (a) Hg(l) Hg(g)
6.1 Define these terms: system, surroundings, open (b) 3O2(g) 2O3(g)
system, closed system, isolated system, thermal (c) CuSO4 • 5H2O(s) CuSO4(s) + 5H2O(g)
energy, chemical energy, potential energy, kinetic
(d) H2(g) + F2(g) 2HF(g)
energy, law of conservation of energy.
At constant pressure, in which of the reactions is
6.2 What is heat? How does heat differ from thermal
work done by the system on the surroundings? By the
energy? Under what condition is heat transferred
surroundings on the system? In which of them is no
from one system to another?
work done?
6.3 What are the units for energy commonly
employed in chemistry?
Problems
6.4 A truck initially traveling at 60 km per hour is
6.15 A sample of nitrogen gas expands in volume
brought to a complete stop at a traffic light. Does this
from 1.6 L to 5.4 L at constant temperature. Calculate
change violate the law of conservation of energy?
the work done in joules if the gas expands (a) against
Explain.
a vacuum, (b) against a constant pressure of 0.80 atm,
6.5 These are various forms of energy: chemical,
and (c) against a constant pressure of 3.7 atm.
heat,
6.16 A gas expands in volume from 26.7 mL to 89.3
light, mechanical, and electrical. Suggest ways of
mL at constant temperature. Calculate the work done
interconverting these forms of energy.
(in joules) if the gas expands (a) against a vacuum,
6.6 Describe the interconversions of forms of energy
(b) against a constant pressure of 1.5 atm, and (c)
occurring in these processes: (a) You throw a softball
against a constant pressure of 2.8 atm.
up into the air and catch it. (b) You switch on a
6.17 A gas expands and does P-V work on the
flashlight. (c) You ride the ski lift to the top of the
surroundings equal to 325 J. At the same time, it
hill and then ski down. (d) You strike a match and let
absorbs 127 J of heat from the surroundings.
it burn down.
Calculate the change in energy of the gas.
6.18 The work done to compress a gas is 74 J. As a 6.26 Determine the amount of heat (in kJ) given off
result, 26 J of heat is given off to the surroundings. when 1.26 3 104 g of NO2 are produced according to
Calculate the change in energy of the gas. the equation
6.19 Calculate the work done when 50.0 g of tin 2NO(g) + O2(g) 2NO2(g)
dissolves in excess acid at 1.00 atm and 25°C: ΔH=-114.6 kJ/mol
Sn(s) + 2H+(aq) Sn2+(aq) + H2(g) 6.27 Consider the reaction
Assume ideal gas behavior. 2H2O(g) 2H2(g) + O2(g)
6.20 Calculate the work done in joules when 1.0 mole ΔH = 483.6 kJ/mol
of water vaporizes at 1.0 atm and 100°C. Assume that If 2.0 moles of H2O(g) are converted to H2(g) and
the volume of liquid water is negligible compared O2(g) against a pressure of 1.0 atm at 125°C, what is
with that of steam at 100°C, and ideal gas behavior. DU for this reaction?
6.28 Consider the reaction
Enthalpy of Chemical Reactions H2(g) + Cl2(g) 2HCl(g)
Review Questions ΔH=-184.6 kJ/mol
6.21 Define these terms: enthalpy, enthalpy of If 3 moles of H2 react with 3 moles of Cl2 to form
reaction. Under what condition is the heat of a HCl, calculate the work done (in joules) against a
reaction equal to the enthalpy change of the same pressure of 1.0 atm at 25°C. What is ΔU for this
reaction? reaction? Assume the reaction goes to completion.
6.22 In writing thermochemical equations, why is it Calorimetry
important to indicate the physical state (that is, Review Questions
gaseous, liquid, solid, or aqueous) of each substance? 6.29 What is the difference between specific heat and
6.23 Explain the meaning of this thermochemical heat capacity? What are the units for these two
equation: quantities? Which is the intensive property and which
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) is the extensive property?
ΔH = -904 kJ/mol 6.30 Define calorimetry and describe two commonly
6.24 Consider this reaction: used calorimeters. In a calorimetric measurement,
2CH3OH(l) + 3O2(g) 4H2O(l) + 2CO2(g) why is it important that we know the heat capacity
ΔH = -1452.8 kJ/mol of the calorimeter? How is this value determined?
What is the value of DH if (a) the equation is Problems
multiplied throughout by 2, (b) the direction of the 6.31 Consider the following data:
reaction is reversed so that the products become the Metal Al Cu
reactants and vice versa, (c) water vapor instead of Mass (g) 10 30
liquid water is formed as the product? Specific heat (J/g•°C) 0.900 0.385
6.23 Explain the meaning of this thermochemical Temperature (°C) 40 60
equation:
4NH3(g) + 5O2(g) 4NO(g) +6H2O(g) When these two metals are placed in contact, which
ΔH = -904 kJ/mol of the following will take place?
6.24 Consider this reaction: (a) Heat will flow from Al to Cu because Al has a
2CH3OH(l) + 3O2(g) 4H2O(l) + 2CO2(g) larger specific heat.
ΔH = -1452.8 kJ/mol (b) Heat will flow from Cu to Al because Cu has a
What is the value of ΔH if (a) the equation is larger mass.
multiplied throughout by 2, (b) the direction of the (c) Heat will flow from Cu to Al because Cu has a
reaction is reversed so that the products become the larger heat capacity.
reactants and vice versa, (c) water vapor instead of (d) Heat will flow from Cu to Al because Cu is at a
liquid water is formed as the product? higher temperature.
Problems (e) No heat will flow in either direction.
6.25 The first step in the industrial recovery of zinc 6.32 A piece of silver of mass 362 g has a heat
from the zinc sulfide ore is roasting, that is, the capacity of 85.7 J/°C. What is the specific heat of
conversion of ZnS to ZnO by heating: silver?
2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g) 6.33 A 6.22-kg piece of copper metal is heated from
ΔH = -879 kJ/mol 20.5°C to 324.3°C. Calculate the heat absorbed (in
Calculate the heat evolved (in kJ) per gram of ZnS kJ) by the metal.
roasted. 6.34 Calculate the amount of heat liberated (in kJ)
from 366 g of mercury when it cools from 77.0°C to
12.0°C.
6.35 A sheet of gold weighing 10.0 g and at a values. H2O2(l) has a negative ΔH°f (see Table 6.4).
temperature of 18.0°C is placed flat on a sheet of iron Why, then, does H2O2(l) have a tendency to
weighing 20.0 g and at a temperature of 55.6°C. decompose to H2O(l) and O2(g)?
What is the final temperature of the combined 6.50 Suggest ways (with appropriate equations) that
metals? Assume that no heat is lost to the would enable you to measure the ΔH°f values of
surroundings. (Hint: The heat gained by the gold Ag2O(s) and CaCl2(s) from their elements. No
must be equal to the heat lost by the iron. The calculations are necessary.
specific heats of the metals are given in Table 6.2.) 6.51 Calculate the heat of decomposition for this
6.36 To a sample of water at 23.4°C in a constant- process at constant pressure and 25°C:
pressure calorimeter of negligible heat capacity is CaCO3(s) CaO(s) + CO2(g)
added a 12.1-g piece of aluminum whose temperature (Look up the standard enthalpy of formation of the
is 81.7°C. If the final temperature of water is 24.9°C, reactant and products in Table 6.4.)
calculate the mass of the water in the calorimeter. 6.52 The standard enthalpies of formation of ions in
(Hint: See Table 6.2.) aqueous solutions are obtained by arbitrarily
6.37 A 0.1375-g sample of solid magnesium is assigning a value of zero to H+ ions; that is,
burned in a constant-volume bomb calorimeter that ΔH°f [H+(aq)] = 0.
has a heat capacity of 3024 J/°C. The temperature (a) For the following reaction
increases by 1.126°C. Calculate the heat given off by H2O
the burning Mg, in kJ/g and in kJ/mol. HCl(g) H+(aq) + Cl-(aq)
6.38 A quantity of 85.0 mL of 0.900 M HCl is mixed ΔH° = -74.9 kJ/mol
with 85.0 mL of 0.900 M KOH in a constant-pressure calculate ΔH°f for the Cl- ions.
calorimeter that has a heat capacity of 325 J/°C. If the (b) Given that ΔH°f for OH- ions is -229.6 kJ/mol,
initial temperatures of both solutions are the same at calculate the enthalpy of neutralization when 1 mole
18.24°C, what is the final temperature of the mixed of a strong monoprotic acid (such as HCl) is titrated
solution? The heat of neutralization is 256.2 kJ/mol. by 1 mole of a strong base (such as KOH) at 25°C.
Assume the density and specific heat of the solutions 6.53 Calculate the heats of combustion for the
are the same as those for water. following reactions from the standard enthalpies of
Standard Enthalpy of Formation and Reaction formation listed in Appendix 3:
Review Questions
(a) 2H2(g) + O2(g) 2H2O(l)
6.39 What is meant by the standard-state condition?
6.40 How are the standard enthalpies of an element (b) 2C2H2(g) +5O2(g) 4CO2(g) +2H2O(l)
and of a compound determined? 6.54 Calculate the heats of combustion for the
6.41 What is meant by the standard enthalpy of a following reactions from the standard enthalpies of
reaction? formation listed in Appendix 3:
6.42 Write the equation for calculating the enthalpy (a) C2H4(g) +3O2(g) 2CO2(g) + 2H2O(l)
of a reaction. Define all the terms. (b) 2H2S(g) + 3O2(g) 2H2O(l) + 2SO2(g)
6.43 State Hess’s law. Explain, with one example, the 6.55 Methanol, ethanol, and n-propanol are three
usefulness of Hess’s law in thermochemistry. common alcohols. When 1.00 g of each of these
6.44 Describe how chemists use Hess’s law to alcohols is burned in air, heat is liberated as shown
determine the ΔH°f of a compound by measuring its by the following data: (a) methanol (CH3OH), 222.6
heat (enthalpy) of combustion. kJ; (b) ethanol (C2H5OH), 229.7 kJ; (c) n-propanol
Problems (C3H7OH), 233.4 kJ. Calculate the heats of
6.45 Which of the following standard enthalpy of combustion of these alcohols in kJ/mol.
formation values is not zero at 25°C? Na(s), Ne(g), 6.56 The standard enthalpy change for the following
CH4(g), S8(s), Hg(l), H(g). reaction is 436.4 kJ/mol:
6.46 The ΔH°f values of the two allotropes of H2(g) H(g) + H(g)
oxygen, O2 and O3, are 0 and 142.2 kJ/mol, Calculate the standard enthalpy of formation of
respectively, at 25°C. Which is the more stable form atomic hydrogen (H).
at this temperature? 6.57 From the standard enthalpies of formation,
6.47 Which is the more negative quantity at 25°C: calculate DH°rxn for the reaction
ΔH°f for H2O(l) or ΔH°f for H2O(g)? C6H12(l) + 9O2(g) 6CO2(g) + 6H2O(l)
6.48 Predict the value of ΔH°f (greater than, less For C6H12(l), ΔH°f = -151.9 kJ/mol.
than, or equal to zero) for these elements at 25°C: (a) 6.58 Pentaborane-9, B5H9, is a colorless, highly
Br2(g); Br2(l). (b) I2(g); I2(s). reactive liquid that will burst into flame when
6.49 In general, compounds with negative ΔH°f exposed to oxygen. The reaction is
values are more stable than those with positive ΔH°f
2B5H9(l) + 12O2(g) 5B2O3(s) + 9H2O(l) Heat of Solution and Dilution
Calculate the kilojoules of heat released per gram of Review Questions
the compound reacted with oxygen. The standard 6.65 Define the following terms: enthalpy of solution,
enthalpy of formation of B5H9 is 73.2 kJ/mol. heat of hydration, lattice energy, heat of dilution.
6.59 Determine the amount of heat (in kJ) given off 6.66 Why is the lattice energy of a solid always a
when 1.26 x 104 g of ammonia are produced positive quantity? Why is the hydration of ions
according to the equation always a negative quantity?
N2(g) + 3H2(g) 2NH3(g) 6.67 Consider two ionic compounds A and B. A has a
ΔH°rxn = -92.6 kJ/mol larger lattice energy than B. Which of the two
Assume that the reaction takes place under standard compounds is more stable?
state conditions at 25°C. 6.68 Mg2+ is a smaller cation than Na+ and also
6.60 At 850°C, CaCO3 undergoes substantial carries more positive charge. Which of the two
decomposition to yield CaO and CO2. Assuming that species has a larger hydration energy (in kJ/mol)?
the ΔH°f values of the reactant and products are the Explain.
same at 850°C as they are at 25°C, calculate the 6.69 Consider the dissolution of an ionic compound
enthalpy change (in kJ) if 66.8 g of CO2 are produced such as potassium fluoride in water. Break the
in one reaction. process into the following steps: separation of the
6.61 From these data, cations and anions in the vapor phase and the
hydration of the ions in the aqueous medium. Discuss
S(rhombic) + O2(g) SO2(g)
the energy changes associated with each step. How
ΔH°rxn = -296.06 kJ/mol
does the heat of solution of KF depend on the relative
S(monoclinic) + O2(g) SO2(g) magnitudes of these two quantities? On what law is
ΔH°rxn = -296.36 kJ/mol the relationship based?
calculate the enthalpy change for the transformation 6.70 Why is it dangerous to add water to a
S(rhombic) !S(monoclinic) concentrated acid such as sulfuric acid in a dilution
(Monoclinic and rhombic are different allotropic process?
forms of elemental sulfur.) Additional Problems
6.62 From the following data, 6.71 Which of the following does not have ΔH°f
C(graphite) + O2(g) CO2(g) = 0 at 25°C?
ΔH°rxn = -393.5 kJ/mol He(g) Fe(s) Cl(g) S8(s) O2(g) Br2(l)
H2(g) + 1/2O2(g) H2O(l) 6.72 Calculate the expansion work done when 3.70
ΔH°rxn = -285.8 kJ/mol moles of ethanol are converted to vapor at its boiling
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) point (78.3°C) and 1.0 atm.
ΔH°rxn = -3119.6 kJ/mol 6.73 The convention of arbitrarily assigning a zero
calculate the enthalpy change for the reaction enthalpy value for the most stable form of each
2C(graphite) + 3H2(g) C2H6(g) element in the standard state at 25°C is a convenient
6.63 From the following heats of combustion, way of dealing with enthalpies of reactions. Explain
why this convention cannot be applied to nuclear
CH3OH(l) + 3/2O2(g) CO2(g) + 2H2O(l)
reactions.
ΔH°rxn = -726.4 kJ/mol
6.74 Given the thermochemical equations:
C(graphite) + O2(g) CO2(g)
Br2(l) + F2(g) 2BrF(g)
ΔH°rxn = -393.5 kJ/mol
ΔH° = -188 kJ/mol
H2(g) + 1/2O2(g) H2O(l)
Br2(l) + 3F2(g) 2BrF3(g)
ΔH°rxn = -285.8 kJ/mol
ΔH° = -768 kJ/mol
calculate the enthalpy of formation of methanol
calculate the ΔH°rxn for the reaction
(CH3OH) from its elements:
BrF(g) + F2(g) BrF3(g)
C(graphite) + 2H2(g) + 1/2O2(g) CH3OH(l)
6.75 The standard enthalpy change ΔH° for the
6.64 Calculate the standard enthalpy change for the
thermal decomposition of silver nitrate according to
reaction
the following equation is 178.67 kJ:
2Al(s) + Fe2O3(s) 2Fe(s) + Al2O3(s)
AgNO3(s) AgNO2(s) + 12O2(g)
given that
The standard enthalpy of formation of AgNO 3(s) is
2Al(s) + 3/2O2(g) Al2O3(s) -123.02 kJ/mol. Calculate the standard enthalpy of
ΔH°rxn = -1669.8 kJ/mol formation of AgNO2(s).
2Fe(s) + 3/2O2(g) Fe2O3(s) 6.76 Hydrazine, N2H4, decomposes according to the
ΔH°rxn = -822.2 kJ/mol following reaction:
3N2H4(l) 4NH3(g) + N2(g) Br2(g) 2Br(g) ΔH° = 192.5 kJ/mol
(a) Given that the standard enthalpy of formation of H2(g) + Br2(g) 2HBr(g)
hydrazine is 50.42 kJ/mol, calculate ΔH° for its ΔH° = -72.4 kJ/mol
decomposition. Calculate ΔH° for the reaction
(b) Both hydrazine and ammonia burn in oxygen to H(g) + Br(g) HBr(g)
produce H2O(l) and N2(g). Write balanced equations 6.85 A gaseous mixture consists of 28.4 mole percent
for each of these processes and calculate ΔH° for of hydrogen and 71.6 mole percent of methane. A
each of them. On a mass basis (per kg), would 15.6-L gas sample, measured at 19.4°C and 2.23 atm,
hydrazine or ammonia be the better fuel? is burned in air. Calculate the heat released.
6.77 A quantity of 2.00 3 102 mL of 0.862 M HCl is 6.86 When 2.740 g of Ba reacts with O2 at 298 K and
mixed with an equal volume of 0.431 M Ba(OH)2 in a 1 atm to form BaO, 11.14 kJ of heat are released.
constant-pressure calorimeter of negligible heat What is ΔH° for BaO?
capacity. The initial temperature of the HCl and 6.87 Methanol (CH3OH) is an organic solvent and is
Ba(OH)2 solutions is the same at 20.48°C, For the also used as a fuel in some automobile engines. From
process the following data, calculate the standard enthalpy of
H+(aq) + OH-(aq) H2O(l) formation of methanol:
the heat of neutralization is 256.2 kJ/mol. What is the 2CH3OH(l) + 3O2(g) 2CO2(g) + 4H2O(l)
final temperature of the mixed solution? ΔH°rxn = -1452.8 kJ/mol
6.78 A 3.53-g sample of ammonium nitrate 6.88 A 44.0-g sample of an unknown metal at 99.0°C
(NH4NO3) was added to 80.0 mL of water in a was placed in a constant-pressure calorimeter
constant-pressure calorimeter of negligible heat containing 80.0 g of water at 24.0°C. The final
capacity. As a result, the temperature of the water temperature of the system was found to be 28.4°C.
decreased from 21.6°C to 18.1°C. Calculate the heat Calculate the specific heat of the metal. (The heat
of solution (ΔHsoln) of ammonium nitrate. capacity of the calorimeter is 12.4 J/°C.)
6.79 Consider the reaction 6.89 Using the data in Appendix 3, calculate the
N2(g) + 3H2(g) 2NH3(g) enthalpy change for the gaseous reaction shown here.
ΔH°rxn = -92.6 kJ/mol (Hint: First determine the limiting reagent.)
If 2.0 moles of N2 react with 6.0 moles of H2 to form
NH3, calculate the work done (in joules) against a
pressure of 1.0 atm at 25°C. What is ΔU for this
reaction? Assume the reaction goes to completion.
6.80 Calculate the heat released when 2.00 L of
Cl2(g) with a density of 1.88 g/L react with an excess
of sodium metal at 25°C and 1 atm to form sodium
chloride.
6.81 Photosynthesis produces glucose, C6H12O6, and
oxygen from carbon dioxide and water:
6CO2 + 6H2O C6H12O6 + 6O2 6.90 Producer gas (carbon monoxide) is prepared by
(a) How would you determine experimentally the passing air over red-hot coke:
ΔH°rxn value for this reaction? (b) Solar radiation C(s) + 1/2O2(g) CO(g)
produces about 7.0 x 1014 kg glucose a year on Earth. Water gas (mixture of carbon monoxide and
What is the corresponding ΔH° change? hydrogen) is prepared by passing steam over red-hot
6.82 A 2.10-mole sample of crystalline acetic acid, coke:
initially at 17.0°C, is allowed to melt at 17.0°C and is
C(s) + H2O(g) CO(g) + H2(g)
then heated to 118.1°C (its normal boiling point) at
For many years, both producer gas and water gas
1.00 atm. The sample is allowed to vaporize at
were used as fuels in industry and for domestic
118.1°C and is then rapidly quenched to 17.0°C, so
cooking. The large-scale preparation of these gases
that it recrystallizes. Calculate ΔH° for the total
was carried out alternately, that is, first producer gas,
process as described.
then water gas, and so on. Using thermochemical
6.83 Calculate the work done in joules by the reaction
reasoning, explain why this procedure was chosen.
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g) 6.91 Compare the heat produced by the complete
when 0.34 g of Na reacts with water to form combustion of 1 mole of methane (CH4) with a mole
hydrogen gas at 0°C and 1.0 atm. of water gas (0.50 mole H2 and 0.50 mole CO) under
6.84 You are given the following data:
H2(g) 2H(g) ΔH° = 436.4 kJ/mol
the same conditions. On the basis of your answer, work done (in joules) by the gas if it expands (a)
would you prefer methane over water gas as a fuel? against a vacuum and (b) against a constant pressure
Can you suggest two other reasons why methane is of 0.20 atm. (c) If the gas in (b) is allowed to expand
preferable to water gas as a fuel? unchecked until its pressure is equal to the external
6.92 The so-called hydrogen economy is based on pressure, what would its final volume be before it
hydrogen produced from water using solar energy. stopped expanding, and what would be the work
The gas may be burned as a fuel: done?
2H2(g) + O2(g) 2H2O(l) 6.101 Calculate the standard enthalpy of formation
A primary advantage of hydrogen as a fuel is that it is for diamond, given that
nonpolluting. A major disadvantage is that it is a gas C(graphite) + O2(g) CO2(g)
and therefore is harder to store than liquids or solids. ΔH° = -393.5 kJ/mol
Calculate the volume of hydrogen gas at 25°C and C(diamond) + O2(g) CO2(g)
1.00 atm required to produce an amount of energy ΔH° = 2395.4 kJ/mol
equivalent to that produced by the combustion of a 6.102 (a) For most efficient use, refrigerator freezer
gallon of octane (C8H18). The density of octane is compartments should be fully packed with food.
2.66 kg/gal, and its standard enthalpy of formation is What is the thermochemical basis for this
-249.9 kJ/mol. recommendation? (b) Starting at the same
6.93 Ethanol (C2H5OH) and gasoline (assumed to be temperature, tea and coffee remain hot longer in a
all octane, C8H18) are both used as automobile fuel. If thermal flask than chicken noodle soup. Explain.
gasoline is selling for $4.50/gal, what would the price 6.103 Calculate the standard enthalpy change for the
of ethanol have to be in order to provide the same fermentation process. (See Problem 3.72.)
amount of heat per dollar? The density and ΔH°f of 6.104 Portable hot packs are available for skiers and
octane are 0.7025 g/mL and -249.9 kJ/mol and of people engaged in other outdoor activities in a cold
ethanol are 0.7894 g/mL and -277.0 kJ/mol, climate. The air-permeable paper packet contains a
respectively. 1 gal 5 3.785 L. mixture of powdered iron, sodium chloride, and other
6.94 The combustion of what volume of ethane components, all moistened by a little water. The
(C2H6), measured at 23.0°C and 752 mmHg, would exothermic reaction that produces the heat is a very
be required to heat 855 g of water from 25.0°C to common one—the rusting of iron:
98.0°C? 4Fe(s) + 3O2(g) 2Fe2O3(s)
6.95 If energy is conserved, how can there be an When the outside plastic envelope is removed, O 2
energy crisis? molecules penetrate the paper, causing the reaction to
6.96 The heat of vaporization of a liquid (ΔHvap) is begin. A typical packet contains 250 g of iron to
the energy required to vaporize 1.00 g of the liquid at warm your hands or feet for up to 4 hours. How much
its boiling point. In one experiment, 60.0 g of liquid heat (in kJ) is produced by this reaction? (Hint: See
nitrogen (boiling point -196°C) are poured into a Appendix 3 for ΔH°f values.)
Styrofoam cup containing 2.00 x 102 g of water at 6.105 A person ate 0.50 pound of cheese (an energy
55.3°C. Calculate the molar heat of vaporization of intake of 4000 kJ). Suppose that none of the energy
liquid nitrogen if the final temperature of the water is was stored in his body. What mass (in grams) of
41.0°C. water would he need to perspire in order to maintain
6.97 Explain the cooling effect experienced when his original temperature? (It takes 44.0 kJ to vaporize
ethanol is rubbed on your skin, given that 1 mole of water.)
C2H5OH(l) C2H5OH(g) ΔH° = 42.2 kJ/mol 6.106 The total volume of the Pacific Ocean is
6.98 For which of the following reactions does estimated to be 7.2 x 108 km3. A medium-sized
ΔH°rxn = ΔH°f ? atomic bomb produces 1.0 x 1015 J of energy upon
(a) H2(g) + S(rhombic) H2S(g) explosion. Calculate the number of atomic bombs
(b) C(diamond) + O2(g) CO2(g) needed to release enough energy to raise the
(c) H2(g) + CuO(s) H2O(l) + Cu(s) temperature of the water in the Pacific Ocean by 1°C.
6.107 A 19.2-g quantity of dry ice (solid carbon
(d) O(g) + O2(g) O3(g)
dioxide) is allowed to sublime (evaporate) in an
6.99 Calculate the work done (in joules) when 1.0
apparatus like the one shown in Figure 6.5. Calculate
mole of water is frozen at 0°C and 1.0 atm. The
the expansion work done against a constant external
volumes of one mole of water and ice at 0°C are
pressure of 0.995 atm and at a constant temperature
0.0180 L and 0.0196 L, respectively.
of 22°C. Assume that the initial volume of dry ice is
6.100 A quantity of 0.020 mole of a gas initially at
negligible and that CO2 behaves like an ideal gas.
0.050 L and 20°C undergoes a constant-temperature
expansion until its volume is 0.50 L. Calculate the
6.108 The enthalpy of combustion of benzoic acid Fe3+(aq) + 3OH-(aq) Fe(OH)3(s)
(C6H5COOH) is commonly used as the standard for 6.115 An excess of zinc metal is added to 50.0 mL of
calibrating constant-volume bomb calorimeters; its a 0.100 M AgNO3 solution in a constant-pressure
value has been accurately determined to be -3226.7 calorimeter like the one pictured in Figure 6.9. As a
kJ/mol. When 1.9862 g of benzoic acid are burned in result of the reaction
a calorimeter, the temperature rises from 21.84°C to Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s)
25.67°C. What is the heat capacity of the bomb? the temperature rises from 19.25°C to 22.17°C. If the
(Assume that the quantity of water surrounding the heat capacity of the calorimeter is 98.6 J/°C, calculate
bomb is exactly 2000 g.) the enthalpy change for the above reaction on a molar
6.109 The combustion of a 25.0-g gaseous mixture of basis. Assume that the density and specific heat of the
H2 and CH- releases -354 kJ of heat. Calculate the solution are the same as those for water, and ignore
amounts of the gases in grams. the specific heats of the metals.
6.110 Calcium oxide (CaO) is used to remove sulfur 6.116 (a) A person drinks four glasses of cold water
dioxide generated by coal-burning power stations: (3.0°C) every day. The volume of each glass is 2.5 x
2CaO(s) + 2SO2(g) + O2(g) 2CaSO4(s) 102 mL. How much heat (in kJ) does the body have to
Calculate the enthalpy change for this process if supply to raise the temperature of the water to 37°C,
6.6 3 105 g of SO2 are removed by this process every the body temperature? (b) How much heat would
day. your body lose if you were to ingest 8.0 x 102 g of
6.111 Glauber’s salt, sodium sulfate decahydrate (Na- snow at 0°C to quench thirst? (The amount of heat
SO4 •10H2O), undergoes a phase transition (that is, necessary to melt snow is 6.01 kJ/mol.)
melting or freezing) at a convenient temperature of 6.117 A driver’s manual states that the stopping
about 32°C: distance quadruples as the speed doubles; that is, if it
Na2SO4 • 10H2O(s) Na2SO4 • 10H2O(l) takes 30 ft to stop a car moving at 25 mph then it
ΔH° = 74.4 kJ/mol would take 120 ft to stop a car moving at 50 mph.
As a result, this compound is used to regulate the Justify this statement by using mechanics and the first
temperature in homes. It is placed in plastic bags in law of thermodynamics. [Assume that when a car is
the ceiling of a room. During the day, the stopped, its kinetic energy (12 mu2) is totally
endothermic melting process absorbs heat from the converted to heat.]
surroundings, cooling the room. At night, it gives off 6.118 At 25°C, the standard enthalpy of formation of
heat as it freezes. Calculate the mass of Glauber’s salt HF(aq) is given by -320.1 kJ/mol; of OH-(aq), it is
in kilograms needed to lower the temperature of air in -229.6 kJ/mol; of F-(aq), it is -329.1 kJ/mol; and of
a room by 8.2°C at 1.0 atm. The dimensions of the H2O(l), it is -285.8 kJ/mol.
room are 2.80 m x 10.6 m x 17.2 m, the specific heat (a) Calculate the standard enthalpy of neutralization
of air is 1.2 J/g °C, and the molar mass of air may be of HF(aq):
taken as 29.0 g/mol. HF(aq) + OH-(aq) F-(aq) + H2O(l)
6.112 A balloon 16 m in diameter is inflated with (b) Using the value of -56.2 kJ as the standard
helium at 18°C. (a) Calculate the mass of He in the enthalpy change for the reaction
balloon, assuming ideal behavior. (b) Calculate the H+(aq) + OH-(aq) H2O(l)
work done (in joules) during the inflation process if calculate the standard enthalpy change for the
the atmospheric pressure is 98.7 kPa. reaction
6.113 Acetylene (C2H2) can be hydrogenated
HF(aq) H+(aq) + F-(aq)
(reacting with hydrogen) first to ethylene (C 2H4) and
6.119 Why are cold, damp air and hot, humid air
then to ethane (C2H6). Starting with one mole of
more uncomfortable than dry air at the same
C2H2, label the diagram shown here analogous to
temperatures? (The specific heats of water vapor and
Figure 6.10. Use the data in Appendix 3.
air are approximately 1.9 J/g°C and 1.0 J/g°C,
respectively.)
6.120 From the enthalpy of formation for CO2 and the
following information, calculate the standard
enthalpy of formation for carbon monoxide (CO).
CO(g) + 1/2O2(g) CO2(g)
ΔH° = -283.0 kJ/mol
Why can’t we obtain it directly by measuring the
enthalpy of the following reaction?
C(graphite) + 1/2O2(g) CO(g)
6.114 Calculate the ΔH° for the reaction
6.121 A 46-kg person drinks 500 g of milk, which
has a “caloric” value of approximately 3.0 kJ/g. If
only 17 percent of the energy in milk is converted to
mechanical work, how high (in meters) can the
person climb based on this energy intake? [Hint: The
work done in ascending is given by mgh, where m is
the mass (in kilograms), g the gravitational
acceleration (9.8 m/s2), and h the height (in meters).] 6.128 How much heat is required to decompose 89.7
6.122 The height of Niagara Falls on the American g of NH4Cl? (Hint: You may use the enthalpy of
side is 51 m. (a) Calculate the potential energy of 1.0 formation values at 25°C for the calculation.)
g of water at the top of the falls relative to the ground 6.129 A gas company in Massachusetts charges $1.30
level. (b) What is the speed of the falling water if all for 15 ft3 of natural gas (CH4) measured at 20°C and
of the potential energy is converted to kinetic energy? 1.0 atm. Calculate the cost of heating 200 mL of
(c) What would be the increase in temperature of the water (enough to make a cup of coffee or tea) from
water if all the kinetic energy were converted to heat? 20°C to 100°C. Assume that only 50 percent of the
(See Problem 6.121 for suggestions.) heat generated by the combustion is used to heat the
6.123 In the nineteenth century two scientists named water; the rest of the heat is lost to the surroundings.
Dulong and Petit noticed that for a solid element, the 6.130 Calculate the internal energy of a Goodyear
product of its molar mass and its specific heat is blimp filled with helium gas at 1.2 x 105 Pa. The
approximately 25 J/°C. This observation, now called volume of the blimp is 5.5 x 103 m3. If all the energy
Dulong and Petit’s law, was used to estimate the were used to heat 10.0 tons of copper at 21°C,
specific heat of metals. Verify the law for the metals calculate the final temperature of the metal. (Hint:
listed in Table 6.2. The law does not apply to one of See Section 5.7 for help in calculating the internal
the metals. Which one is it? Why? energy of a gas. 1 ton = 9.072 x 105 g.)
6.124 Determine the standard enthalpy of formation 6.131 Decomposition reactions are usually
of ethanol (C2H5OH) from its standard enthalpy of endothermic, whereas combination reactions are
combustion (-1367.4 kJ/mol). usually exothermic. Give a qualitative explanation for
6.125 Acetylene (C2H2) and benzene (C6H6) have the these trends.
same empirical formula. In fact, benzene can be made 6.132 Acetylene (C2H2) can be made by reacting
from acetylene as follows: calcium carbide (CaC2) with water. (a) Write an
3C2H2(g) C6H6(l) equation for the reaction. (b) What is the maximum
The enthalpies of combustion for C2H2 and C6H6 are amount of heat (in joules) that can be obtained from
-1299.4 kJ/mol and 23267.4 kJ/mol, respectively. the combustion of acetylene, starting with 74.6 g of
Calculate the standard enthalpies of formation of CaC2?
C2H2 and C6H6 and hence the enthalpy change for the 6.133 The average temperature in deserts is high
formation of C6H6 from C2H2. during the day but quite cool at night, whereas that in
6.126 Ice at 0°C is placed in a Styrofoam cup regions along the coastline is more moderate.
containing 361 g of a soft drink at 23°C. The specific Explain.
heat of the drink is about the same as that of water. 6.134 When 1.034 g of naphthalene (C10H8) are
Some ice remains after the ice and soft drink reach an burned in a constant-volume bomb calorimeter at 298
equilibrium temperature of 0°C. Determine the mass K, 41.56 kJ of heat are evolved. Calculate ΔU and
of ice that has melted. Ignore the heat capacity of the ΔH for the reaction on a molar basis.
cup. (Hint: It takes 334 J to melt 1 g of ice at 0°C.) 6.135 From a thermochemical point of view, explain
6.127 After a dinner party, the host performed the why a carbon dioxide fire extinguisher or water
following trick. First, he blew out one of the burning should not be used on a magnesium fire.
candles. He then quickly brought a lighted match to 6.136 Calculate the Δ U for the following reaction at
about 1 in above the wick. To everyone’s surprise, 298 K:
the candle was relighted. Explain how the host was 2H2(g) + O2(g) 2H2O(l)
able to accomplish the task without touching the 6.137 Lime is a term that includes calcium oxide
wick. (CaO, also called quicklime) and calcium hydroxide
[Ca(OH)2, also called slaked lime]. It is used in the
steel industry to remove acidic impurities, in
airpollution control to remove acidic oxides such as
SO2, and in water treatment. Quicklime is made temperature, (b) adding heat to a system does not
industrially by heating limestone (CaCO3) above change (raise) its temperature, and (c) a system’s
2000°C: temperature is changed even though no heat is added
CaCO3(s) CaO(s) + CO2(g) or removed from it.
ΔH° = 177.8 kJ/mol 6.143 From the following data, calculate the heat of
Slaked lime is produced by treating quicklime with solution for KI:
water: NaCl NaI KCl KI
CaO(s) + H2O(l) Ca(OH)2(s) Lattice Energy (kJ/mol) 788 686 699 632
ΔH° = -65.2 kJ/mol Heat of solution 4.0 -5.1 17. 7
The exothermic reaction of quicklime with water and 2
the rather small specific heats of both quicklime
(0.946 J/g°C) and slaked lime (1.20 J/g°C) make it 6.144 Starting at A, an ideal gas undergoes a cyclic
hazardous to store and transport lime in vessels made process involving expansion and compression, as
of wood. Wooden sailing ships carrying lime would shown here. Calculate the total work done. Does your
occasionally catch fire when water leaked into the result support the notion that work is not a state
hold. (a) If a 500-g sample of water reacts with an function?
equimolar amount of CaO (both at an initial
temperature of 25°C), what is the final temperature of
the product, Ca(OH)2? Assume that the product
absorbs all of the heat released in the reaction. (b)
Given that the standard enthalpies of formation of
CaO and H2O are -35.6 kJ/mol and -285.8 kJ/mol,
respectively, calculate the standard enthalpy of
formation of Ca(OH)2.
6.138 A 4.117-g impure sample of glucose (C 6H12O6)
was burned in a constant-volume calorimeter having
a heat capacity of 19.65 kJ/°C. If the rise in
6.145 For reactions in condensed phases (liquids and
temperature is 3.134°C, calculate the percent by mass
solids), the difference between ΔH and ΔU is usually
of the glucose in the sample. Assume that the
quite small. This statement holds for reactions carried
impurities are unaffected by the combustion process.
out under atmospheric conditions. For certain
See Appendix 3 for thermodynamic data.
geochemical processes, however, the external
6.139 Construct a table with the headings q, w, ΔU,
pressure may be so great that ΔH and ΔU can differ
and ΔH. For each of the following processes, deduce
by a significant amount. A well-known example is
whether each of the quantities listed is positive (1),
the slow conversion of graphite to diamond under
negative (2), or zero (0). (a) Freezing of benzene. (b)
Earth’s surface. Calculate (ΔH - ΔU) for the
Compression of an ideal gas at constant temperature.
conversion of 1 mole of graphite to 1 mole of
(c) Reaction of sodium with water. (d) Boiling liquid
diamond at a pressure of 50,000 atm. The densities of
ammonia. (e) Heating a gas at constant volume. (f)
graphite and diamond are 2.25 g/cm3 and 3.52
Melting of ice.
g/cm3, respectively.
6.140 The combustion of 0.4196 g of a hydrocarbon
6.146 The diagrams shown here represent various
releases 17.55 kJ of heat. The masses of the products
are CO2 = 1.419 g and H2O = 0.290 g. (a) What is the physical and chemical processes. (a) 2A(g)
empirical formula of the compound? (b) If the A2(g).
approximate molar mass of the compound is 76 g, (b) MX(s) M+(aq) + X-(aq). (c) AB(g) +
calculate its standard enthalpy of formation. C(g) AC(g) + B(g). (d) B(l) B(g).
6.141 Metabolic activity in the human body releases Predict whether the situations shown are endothermic
approximately 1.0 x 104 kJ of heat per day. Assuming or exothermic. Explain why in some cases no clear
the body is 50 kg of water, how much would the body conclusions can be made.
temperature rise if it were an isolated system? How
much water must the body eliminate as perspiration
to maintain the normal body temperature (98.6°F)?
Comment on your results. The heat of vaporization of
water may be taken as 2.41 kJ/g.
6.142 Give an example for each of the following
situations: (a) Adding heat to a system raises its
 6.155 A press release announcing a new fuel-cell car
to the public stated that hydrogen is “relatively
cheap” and “some stations in California sell hydrogen
for $5 a kilogram. A kg has the same energy as a
gallon of gasoline, so it’s like paying $5 a gallon. But
you go two to three times as far on the hydrogen.”
Analyze this claim.
6.156 We hear a lot about how the burning of
hydrocarbons produces the greenhouse gas CO2, but
what about the effect of increasing energy
consumption on the amount of oxygen in the
6.147 A 20.3-g sample of an unknown metal and a atmosphere required to sustain life. The figure shows
28.5-g sample of copper, both at 80.6°C, are added to past and projected energy world consumption. (a)
100 g of water at 11.2°C in a constant-pressure How many moles of oxygen would be required to
calorimeter of negligible heat capacity. If the final generate the additional energy expenditure for the
temperature of the metals and water is 13.7°C, next decade? (b) What would be the resulting
determine the specific heat of the unknown metal. decrease in atmospheric oxygen?
Interpreting, Modeling & Estimating
6.148 For most biological processes, ΔH < ΔU.
Explain.
6.149 Estimate the potential energy expended by an
average adult male in going from the ground to the
top floor of the Empire State Building using the
staircase.
6.150 The fastest serve in tennis is about 150 mph.
Can the kinetic energy of a tennis ball traveling at
this speed be sufficient to heat 1 mL of water by
30°C?
6.151 Can the total energy output of the sun in one
second be sufficient to heat all of the ocean water on
Earth to its boiling point?
6.152 It has been estimated that 3 trillion standard
cubic feet of methane is released into the atmosphere
every year. Capturing that methane would provide a
source of energy, and it would also remove a potent
greenhouse gas from the atmosphere (methane is 25
times more effective at trapping heat than an equal
number of molecules of carbon dioxide). Standard
cubic feet is measured at 60°F and 1 atm. Determine
the amount of energy that could be obtained by
combustion of the methane that escapes each year.
6.153 Biomass plants generate electricity from waste
material such as wood chips. Some of these plants
convert the feedstock to ethanol (C2H5OH) for later
use as a fuel. (a) How many grams of ethanol can be
produced from 1.0 ton of wood chips, if 85 percent of
the carbon is converted to C2H5OH? (b) How much
energy would be released by burning the ethanol
obtained from 1.0 ton of wood chips? (Hint: Treat the
wood chips as cellulose.)
6.154 Suppose an automobile carried hydrogen gas in
its fuel tank instead of gasoline. At what pressure
would the hydrogen gas need to be kept for the tank
to contain an equivalent amount of chemical energy
as a tank of gasoline?