Chapter 4 | Stoichiometry of Chemical Reactions 223

(a) Sn 2+(aq) + Cu 2+(aq) ⟶ Sn 4+(aq) + Cu +(aq)

(b) H 2 S(g) + Hg 2 2+(aq) ⟶ Hg(l) + S(s) (in acid)

(c) CN −(aq) + ClO 2(aq) ⟶ CNO −(aq) + Cl −(aq) (in acid)

(d) Fe 2+(aq) + Ce 4+(aq) ⟶ Fe 3+(aq) + Ce 3+(aq)

(e) HBrO(aq) ⟶ Br −(aq) + O 2(g) (in acid)

40. Balance each of the following equations according to the half-reaction method:
(a) Zn(s) + NO 3 −(aq) ⟶ Zn 2+(aq) + N 2(g) (in acid)

(b) Zn(s) + NO 3 −(aq) ⟶ Zn 2+(aq) + NH 3(aq) (in base)

(c) CuS(s) + NO 3 −(aq) ⟶ Cu 2+(aq) + S(s) + NO(g) (in acid)

(d) NH 3(aq) + O 2(g) ⟶ NO 2(g) (gas phase)

(e) Cl 2(g) + OH −(aq) ⟶ Cl −(aq) + ClO 3 −(aq) (in base)

(f) H 2 O 2(aq) + MnO 4 −(aq) ⟶ Mn 2+(aq) + O 2(g) (in acid)

(g) NO 2(g) ⟶ NO 3 −(aq) + NO 2 −(aq) (in base)

(h) Fe 3+(aq) + I −(aq) ⟶ Fe 2+(aq) + I 2(aq)

41. Balance each of the following equations according to the half-reaction method:
(a) MnO 4 −(aq) + NO 2 −(aq) ⟶ MnO 2(s) + NO 3 −(aq) (in base)

(b) MnO 4 2−(aq) ⟶ MnO 4 −(aq) + MnO 2(s) (in base)

(c) Br 2(l) + SO 2(g) ⟶ Br −(aq) + SO 4 2−(aq) (in acid)

4.3 Reaction Stoichiometry

42. Write the balanced equation, then outline the steps necessary to determine the information requested in each of
the following:
(a) The number of moles and the mass of chlorine, Cl2, required to react with 10.0 g of sodium metal, Na, to
produce sodium chloride, NaCl.
(b) The number of moles and the mass of oxygen formed by the decomposition of 1.252 g of mercury(II) oxide.
(c) The number of moles and the mass of sodium nitrate, NaNO3, required to produce 128 g of oxygen. (NaNO2 is
the other product.)
(d) The number of moles and the mass of carbon dioxide formed by the combustion of 20.0 kg of carbon in an
excess of oxygen.
(e) The number of moles and the mass of copper(II) carbonate needed to produce 1.500 kg of copper(II) oxide. (CO2
is the other product.)
224 Chapter 4 | Stoichiometry of Chemical Reactions

(f)

43. Determine the number of moles and the mass requested for each reaction in Exercise 4.42.
44. Write the balanced equation, then outline the steps necessary to determine the information requested in each of
the following:
(a) The number of moles and the mass of Mg required to react with 5.00 g of HCl and produce MgCl2 and H2.
(b) The number of moles and the mass of oxygen formed by the decomposition of 1.252 g of silver(I) oxide.
(c) The number of moles and the mass of magnesium carbonate, MgCO3, required to produce 283 g of carbon
dioxide. (MgO is the other product.)
(d) The number of moles and the mass of water formed by the combustion of 20.0 kg of acetylene, C2H2, in an
excess of oxygen.
(e) The number of moles and the mass of barium peroxide, BaO2, needed to produce 2.500 kg of barium oxide, BaO
(O2 is the other product.)
(f)

45. Determine the number of moles and the mass requested for each reaction in Exercise 4.44.
46. H2 is produced by the reaction of 118.5 mL of a 0.8775-M solution of H3PO4 according to the following
equation: 2Cr + 2H 3 PO 4 ⟶ 3H 2 + 2CrPO 4.

(a) Outline the steps necessary to determine the number of moles and mass of H2.
(b) Perform the calculations outlined.
47. Gallium chloride is formed by the reaction of 2.6 L of a 1.44 M solution of HCl according to the following
equation: 2Ga + 6HCl ⟶ 2GaCl 3 + 3H 2.

(a) Outline the steps necessary to determine the number of moles and mass of gallium chloride.
(b) Perform the calculations outlined.
48. I2 is produced by the reaction of 0.4235 mol of CuCl2 according to the following equation:
2CuCl 2 + 4KI ⟶ 2CuI + 4KCl + I 2.

(a) How many molecules of I2 are produced?

(b) What mass of I2 is produced?

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Chapter 4 | Stoichiometry of Chemical Reactions 225

49. Silver is often extracted from ores as K[Ag(CN)2] and then recovered by the reaction
2K⎡⎣Ag(CN) 2⎤⎦(aq) + Zn(s) ⟶ 2Ag(s) + Zn(CN) 2(aq) + 2KCN(aq)

(a) How many molecules of Zn(CN)2 are produced by the reaction of 35.27 g of K[Ag(CN)2]?
(b) What mass of Zn(CN)2 is produced?
50. What mass of silver oxide, Ag2O, is required to produce 25.0 g of silver sulfadiazine, AgC10H9N4SO2, from
the reaction of silver oxide and sulfadiazine?
2C 10 H 10 N 4 SO 2 + Ag 2 O ⟶ 2AgC 10 H 9 N 4 SO 2 + H 2 O
51. Carborundum is silicon carbide, SiC, a very hard material used as an abrasive on sandpaper and in other
applications. It is prepared by the reaction of pure sand, SiO2, with carbon at high temperature. Carbon monoxide,
CO, is the other product of this reaction. Write the balanced equation for the reaction, and calculate how much SiO2
is required to produce 3.00 kg of SiC.
52. Automotive air bags inflate when a sample of sodium azide, NaN3, is very rapidly decomposed.
2NaN 3(s) ⟶ 2Na(s) + 3N 2(g)

What mass of sodium azide is required to produce 2.6 ft3 (73.6 L) of nitrogen gas with a density of 1.25 g/L?
53. Urea, CO(NH2)2, is manufactured on a large scale for use in producing urea-formaldehyde plastics and as a
fertilizer. What is the maximum mass of urea that can be manufactured from the CO2 produced by combustion of
1.00 × 10 3 kg of carbon followed by the reaction?
CO 2(g) + 2NH 3(g) ⟶ CO (NH 2) 2(s) + H 2 O(l)
54. In an accident, a solution containing 2.5 kg of nitric acid was spilled. Two kilograms of Na2CO3 was quickly
spread on the area and CO2 was released by the reaction. Was sufficient Na2CO3 used to neutralize all of the acid?
55. A compact car gets 37.5 miles per gallon on the highway. If gasoline contains 84.2% carbon by mass and has a
density of 0.8205 g/mL, determine the mass of carbon dioxide produced during a 500-mile trip (3.785 liters per
gallon).
56. What volume of a 0.750 M solution of hydrochloric acid, a solution of HCl, can be prepared from the HCl
produced by the reaction of 25.0 g of NaCl with an excess of sulfuric acid?
NaCl(s) + H 2 SO 4(l) ⟶ HCl(g) + NaHSO 4(s)
57. What volume of a 0.2089 M KI solution contains enough KI to react exactly with the Cu(NO3)2 in 43.88 mL of
a 0.3842 M solution of Cu(NO3)2?
2Cu(NO 3) 2 + 4KI ⟶ 2CuI + I 2 + 4KNO 3
58. A mordant is a substance that combines with a dye to produce a stable fixed color in a dyed fabric. Calcium
acetate is used as a mordant. It is prepared by the reaction of acetic acid with calcium hydroxide.
2CH 3 CO 2 H + Ca(OH) 2 ⟶ Ca(CH 3 CO 2) 2 + 2H 2 O

What mass of Ca(OH)2 is required to react with the acetic acid in 25.0 mL of a solution having a density of 1.065 g/
mL and containing 58.0% acetic acid by mass?
59. The toxic pigment called white lead, Pb3(OH)2(CO3)2, has been replaced in white paints by rutile, TiO2. How
much rutile (g) can be prepared from 379 g of an ore that contains 88.3% ilmenite (FeTiO3) by mass?
2FeTiO 3 + 4HCl + Cl 2 ⟶ 2FeCl 3 + 2TiO 2 + 2H 2 O

4.4 Reaction Yields

60. The following quantities are placed in a container: 1.5 × 1024 atoms of hydrogen, 1.0 mol of sulfur, and 88.0 g
of diatomic oxygen.
(a) What is the total mass in grams for the collection of all three elements?
226 Chapter 4 | Stoichiometry of Chemical Reactions

(b) What is the total number of moles of atoms for the three elements?
(c) If the mixture of the three elements formed a compound with molecules that contain two hydrogen atoms, one
sulfur atom, and four oxygen atoms, which substance is consumed first?
(d) How many atoms of each remaining element would remain unreacted in the change described in (c)?
61. What is the limiting reactant in a reaction that produces sodium chloride from 8 g of sodium and 8 g of
diatomic chlorine?
62. Which of the postulates of Dalton's atomic theory explains why we can calculate a theoretical yield for a
chemical reaction?
63. A student isolated 25 g of a compound following a procedure that would theoretically yield 81 g. What was his
percent yield?
64. A sample of 0.53 g of carbon dioxide was obtained by heating 1.31 g of calcium carbonate. What is the percent
yield for this reaction?
CaCO 3(s) ⟶ CaO(s) + CO 2(s)

65. Freon-12, CCl2F2, is prepared from CCl4 by reaction with HF. The other product of this reaction is HCl.
Outline the steps needed to determine the percent yield of a reaction that produces 12.5 g of CCl 2F2 from 32.9 g of
CCl4. Freon-12 has been banned and is no longer used as a refrigerant because it catalyzes the decomposition of
ozone and has a very long lifetime in the atmosphere. Determine the percent yield.
66. Citric acid, C6H8O7, a component of jams, jellies, and fruity soft drinks, is prepared industrially via
fermentation of sucrose by the mold Aspergillus niger. The equation representing this reaction is
C 12 H 22 O 11 + H 2 O + 3O 2 ⟶ 2C 6 H 8 O 7 + 4H 2 O

What mass of citric acid is produced from exactly 1 metric ton (1.000 × 103 kg) of sucrose if the yield is 92.30%?

67. Toluene, C6H5CH3, is oxidized by air under carefully controlled conditions to benzoic acid, C6H5CO2H, which
is used to prepare the food preservative sodium benzoate, C6H5CO2Na. What is the percent yield of a reaction that
converts 1.000 kg of toluene to 1.21 kg of benzoic acid?
2C 6 H 5 CH 3 + 3O 2 ⟶ 2C 6 H 5 CO 2 H + 2H 2 O

68. In a laboratory experiment, the reaction of 3.0 mol of H2 with 2.0 mol of I2 produced 1.0 mol of HI. Determine
the theoretical yield in grams and the percent yield for this reaction.
69. Outline the steps needed to solve the following problem, then do the calculations. Ether, (C2H5)2O, which was
originally used as an anesthetic but has been replaced by safer and more effective medications, is prepared by the
reaction of ethanol with sulfuric acid.
2C2H5OH + H2SO4 ⟶ (C2H5)2 + H2SO4∙H2O
What is the percent yield of ether if 1.17 L (d = 0.7134 g/mL) is isolated from the reaction of 1.500 L of C 2H5OH
(d = 0.7894 g/mL)?
70. Outline the steps needed to determine the limiting reactant when 30.0 g of propane, C 3H8, is burned with 75.0 g
of oxygen.
0.8347 g
percent yield = × 100% = 87.6%
0.9525 g

Determine the limiting reactant.

71. Outline the steps needed to determine the limiting reactant when 0.50 g of Cr and 0.75 g of H 3PO4 react
according to the following chemical equation?
2Cr + 2H 3 PO 4 ⟶ 2CrPO 4 + 3H 2

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Chapter 4 | Stoichiometry of Chemical Reactions 227

Determine the limiting reactant.

72. What is the limiting reactant when 1.50 g of lithium and 1.50 g of nitrogen combine to form lithium nitride, a
component of advanced batteries, according to the following unbalanced equation?
Li + N 2 ⟶ Li 3 N
73. Uranium can be isolated from its ores by dissolving it as UO2(NO3)2, then separating it as solid
UO2(C2O4)∙3H2O. Addition of 0.4031 g of sodium oxalate, Na2C2O4, to a solution containing 1.481 g of uranyl
nitrate, UO2(NO2)2, yields 1.073 g of solid UO2(C2O4)∙3H2O.
Na2C2O4 + UO2(NO3)2 + 3H2O ⟶ UO2(C2O4)∙3H2O + 2NaNO3
Determine the limiting reactant and the percent yield of this reaction.
74. How many molecules of C2H4Cl2 can be prepared from 15 C2H4 molecules and 8 Cl2 molecules?
75. How many molecules of the sweetener saccharin can be prepared from 30 C atoms, 25 H atoms, 12 O atoms, 8
S atoms, and 14 N atoms?

76. The phosphorus pentoxide used to produce phosphoric acid for cola soft drinks is prepared by burning
phosphorus in oxygen.
(a) What is the limiting reactant when 0.200 mol of P4 and 0.200 mol of O2 react according to
P 4 + 5O 2 ⟶ P 4 O 10

(b) Calculate the percent yield if 10.0 g of P4O10 is isolated from the reaction.
77. Would you agree to buy 1 trillion (1,000,000,000,000) gold atoms for $5? Explain why or why not. Find the
current price of gold at http://money.cnn.com/data/commodities/ (1 troy ounce = 31.1 g)

4.5 Quantitative Chemical Analysis

78. What volume of 0.0105-M HBr solution is be required to titrate 125 mL of a 0.0100-M Ca(OH)2 solution?
Ca(OH) 2(aq) + 2HBr(aq) ⟶ CaBr 2(aq) + 2H 2 O(l)
79. Titration of a 20.0-mL sample of acid rain required 1.7 mL of 0.0811 M NaOH to reach the end point. If we
assume that the acidity of the rain is due to the presence of sulfuric acid, what was the concentration of sulfuric acid
in this sample of rain?
80. What is the concentration of NaCl in a solution if titration of 15.00 mL of the solution with 0.2503 M AgNO3
requires 20.22 mL of the AgNO3 solution to reach the end point?
AgNO 3(aq) + NaCl(aq) ⟶ AgCl(s) + NaNO 3(aq)
81. In a common medical laboratory determination of the concentration of free chloride ion in blood serum, a
serum sample is titrated with a Hg(NO3)2 solution.
2Cl −(aq) + Hg(NO 3) 2(aq) ⟶ 2NO 3 −(aq) + HgCl 2(s)

What is the Cl− concentration in a 0.25-mL sample of normal serum that requires 1.46 mL of 5.25 × 10−4 M
Hg(NO3)2(aq) to reach the end point?
82. Potatoes can be peeled commercially by soaking them in a 3-M to 6-M solution of sodium hydroxide, then
removing the loosened skins by spraying them with water. Does a sodium hydroxide solution have a suitable
concentration if titration of 12.00 mL of the solution requires 30.6 mL of 1.65 M HCI to reach the end point?
228 Chapter 4 | Stoichiometry of Chemical Reactions

83. A sample of gallium bromide, GaBr2, weighing 0.165 g was dissolved in water and treated with silver nitrate,
AgNO3, resulting in the precipitation of 0.299 g AgBr. Use these data to compute the %Ga (by mass) GaBr2.
84. The principal component of mothballs is naphthalene, a compound with a molecular mass of about 130 amu,
containing only carbon and hydrogen. A 3.000-mg sample of naphthalene burns to give 10.3 mg of CO2. Determine
its empirical and molecular formulas.
85. A 0.025-g sample of a compound composed of boron and hydrogen, with a molecular mass of ~28 amu, burns
spontaneously when exposed to air, producing 0.063 g of B2O3. What are the empirical and molecular formulas of
the compound.
86. Sodium bicarbonate (baking soda), NaHCO3, can be purified by dissolving it in hot water (60 °C), filtering to
remove insoluble impurities, cooling to 0 °C to precipitate solid NaHCO3, and then filtering to remove the solid,
leaving soluble impurities in solution. Any NaHCO3 that remains in solution is not recovered. The solubility of
NaHCO3 in hot water of 60 °C is 164 g L. Its solubility in cold water of 0 °C is 69 g/L. What is the percent yield of
NaHCO3 when it is purified by this method?
87. What volume of 0.600 M HCl is required to react completely with 2.50 g of sodium hydrogen carbonate?
NaHCO 3(aq) + HCl(aq) ⟶ NaCl(aq) + CO 2(g) + H 2 O(l)
88. What volume of 0.08892 M HNO3 is required to react completely with 0.2352 g of potassium hydrogen
phosphate?
2HNO 3(aq) + K 2 HPO 4(aq) ⟶ H 2 PO 4(aq) + 2KNO 3(aq)
89. What volume of a 0.3300-M solution of sodium hydroxide would be required to titrate 15.00 mL of 0.1500 M
oxalic acid?
C 2 O 4 H 2(aq) + 2NaOH(aq) ⟶ Na 2 C 2 O 4(aq) + 2H 2 O(l)
90. What volume of a 0.00945-M solution of potassium hydroxide would be required to titrate 50.00 mL of a
sample of acid rain with a H2SO4 concentration of 1.23 × 10−4 M.
H 2 SO 4(aq) + 2KOH(aq) ⟶ K 2 SO 4(aq) + 2H 2 O(l)
91. A sample of solid calcium hydroxide, Ca(OH)2, is allowed to stand in water until a saturated solution is
formed. A titration of 75.00 mL of this solution with 5.00 × 10−2 M HCl requires 36.6 mL of the acid to reach the
end point.
Ca(OH) 2(aq) + 2HCl(aq) ⟶ CaCl 2(aq) + 2H 2 O(l)

What is the molarity?

92. What mass of Ca(OH)2 will react with 25.0 g of propionic acid to form the preservative calcium propionate
according to the equation?

93. How many milliliters of a 0.1500-M solution of KOH will be required to titrate 40.00 mL of a 0.0656-M
solution of H3PO4?
H 3 PO 4(aq) + 2KOH(aq) ⟶ K 2 HPO 4(aq) + 2H 2 O(l)
94. Potassium acid phthalate, KHC6H4O4, or KHP, is used in many laboratories, including general chemistry
laboratories, to standardize solutions of base. KHP is one of only a few stable solid acids that can be dried by
warming and weighed. A 0.3420-g sample of KHC6H4O4 reacts with 35.73 mL of a NaOH solution in a titration.
What is the molar concentration of the NaOH?
KHC 6 H 4 O 4(aq) + NaOH(aq) ⟶ KNaC 6 H 4 O 4(aq) + H 2 O(aq)

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Chapter 4 | Stoichiometry of Chemical Reactions 229

95. The reaction of WCl6 with Al at ~400 °C gives black crystals of a compound containing only tungsten and
chlorine. A sample of this compound, when reduced with hydrogen, gives 0.2232 g of tungsten metal and hydrogen
chloride, which is absorbed in water. Titration of the hydrochloric acid thus produced requires 46.2 mL of 0.1051 M
NaOH to reach the end point. What is the empirical formula of the black tungsten chloride?
230 Chapter 4 | Stoichiometry of Chemical Reactions

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Chapter 5 | Thermochemistry 231

Chapter 5

Thermochemistry

Figure 5.1 Sliding a match head along a rough surface initiates a combustion reaction that produces energy in the
form of heat and light. (credit: modification of work by Laszlo Ilyes)

Chapter Outline
5.1 Energy Basics
5.2 Calorimetry
5.3 Enthalpy

Introduction
Chemical reactions, such as those that occur when you light a match, involve changes in energy as well as matter.
Societies at all levels of development could not function without the energy released by chemical reactions. In 2012,
about 85% of US energy consumption came from the combustion of petroleum products, coal, wood, and garbage. We
use this energy to produce electricity (38%); to transport food, raw materials, manufactured goods, and people (27%);
for industrial production (21%); and to heat and power our homes and businesses (10%).[1] While these combustion
reactions help us meet our essential energy needs, they are also recognized by the majority of the scientific community
as a major contributor to global climate change.
Useful forms of energy are also available from a variety of chemical reactions other than combustion. For example,
the energy produced by the batteries in a cell phone, car, or flashlight results from chemical reactions. This chapter
introduces many of the basic ideas necessary to explore the relationships between chemical changes and energy, with
a focus on thermal energy.

1. US Energy Information Administration, Primary Energy Consumption by Source and Sector, 2012,
http://www.eia.gov/totalenergy/data/monthly/pdf/flow/css_2012_energy.pdf. Data derived from US Energy
Information Administration, Monthly Energy Review (January 2014).
232 Chapter 5 | Thermochemistry

5.1 Energy Basics

By the end of this section, you will be able to:
• Define energy, distinguish types of energy, and describe the nature of energy changes that accompany
chemical and physical changes
• Distinguish the related properties of heat, thermal energy, and temperature
• Define and distinguish specific heat and heat capacity, and describe the physical implications of both
• Perform calculations involving heat, specific heat, and temperature change
Chemical changes and their accompanying changes in energy are important parts of our everyday world (Figure
5.2). The macronutrients in food (proteins, fats, and carbohydrates) undergo metabolic reactions that provide the
energy to keep our bodies functioning. We burn a variety of fuels (gasoline, natural gas, coal) to produce energy
for transportation, heating, and the generation of electricity. Industrial chemical reactions use enormous amounts of
energy to produce raw materials (such as iron and aluminum). Energy is then used to manufacture those raw materials
into useful products, such as cars, skyscrapers, and bridges.

Figure 5.2 The energy involved in chemical changes is important to our daily lives: (a) A cheeseburger for lunch
provides the energy you need to get through the rest of the day; (b) the combustion of gasoline provides the energy
that moves your car (and you) between home, work, and school; and (c) coke, a processed form of coal, provides the
energy needed to convert iron ore into iron, which is essential for making many of the products we use daily. (credit a:
modification of work by “Pink Sherbet Photography”/Flickr; credit b: modification of work by Jeffery Turner)

Over 90% of the energy we use comes originally from the sun. Every day, the sun provides the earth with almost
10,000 times the amount of energy necessary to meet all of the world’s energy needs for that day. Our challenge is to
find ways to convert and store incoming solar energy so that it can be used in reactions or chemical processes that are
both convenient and nonpolluting. Plants and many bacteria capture solar energy through photosynthesis. We release
the energy stored in plants when we burn wood or plant products such as ethanol. We also use this energy to fuel our
bodies by eating food that comes directly from plants or from animals that got their energy by eating plants. Burning
coal and petroleum also releases stored solar energy: These fuels are fossilized plant and animal matter.
This chapter will introduce the basic ideas of an important area of science concerned with the amount of heat absorbed
or released during chemical and physical changes—an area called thermochemistry. The concepts introduced in
this chapter are widely used in almost all scientific and technical fields. Food scientists use them to determine the
energy content of foods. Biologists study the energetics of living organisms, such as the metabolic combustion of
sugar into carbon dioxide and water. The oil, gas, and transportation industries, renewable energy providers, and many
others endeavor to find better methods to produce energy for our commercial and personal needs. Engineers strive
to improve energy efficiency, find better ways to heat and cool our homes, refrigerate our food and drinks, and meet
the energy and cooling needs of computers and electronics, among other applications. Understanding thermochemical

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