Thermochemistry Cota Cris wel 6a 62 Cel cry cr Cc 67 ey Peete ie Ce eee car eater The analysis of particles formed from burning methane ina lame is performed witha visible laser. AP EES Reactions that release energy are familiar and can be useful. The burning of propane provides heat, which can be used for cooking. Yee there are reactions Which consume energy as well. If you place your hands around container, Which has salt dissolving in water, you may feel a cold sensation—a sign that the dissolving reaction is absorbing heat from your hands (EK 3.6.2; EK5.B.3) Both energy releasing and energy consuming reactions involve the breaking land the formation of chemical bonds. Despite having this in common, one releases energy while the other absorbs it, How can this happen” What makes ‘one reaction type different from the other? Breaking bonds requires an input of energy. Creating new bonds results in an output of energy. The change we fel is the net energy of the two opposing processes (EK.5.C). This net energy isthe heat that cooks the hamburger on {your gril and is the heat loss of your hands to the container of dissolving salt ‘These net energies can be measured through a device called a calorimeter (alori-meter!). Using the Law of Conservation of Energy (EK'SIB2), the energy change of the calorimeter is linked tothe energy change of a reaction (EKSIBA), This energy can be included in an equation representing a reaction and used along with moles and masses to determine the amount of energy released or consumed by a reaction, ‘As you read the chapter, think about these Essential Questions: What is chemical potential energy of atoms? SiC ‘What is the chemical potential energy of molecules? SIDE What is heat? 3102 What is the difference between an exothermic and an endothermic reaction? 502 5, Does adding heat to system change its energy content? What is the direction of energy flow in a chemical reaction? SBS ‘What isthe relationship between energy, work, and heat? SIBID How can a balances! chemical equation be used to determine heats of reaction? LEQ6:1 The Nature of Energy and Types of Energy 231 ‘very chemical reaction obeys two fundamental laws: the law of conservation of mass and be law of conservation of energy. We discussed the mass relationship between reactants and products in Chapter 3; here we will look at the energy changes that accompany chemical reactions Bg The Nature of Energy and Types of Energy nergy” is a much-used term that represents a rather abstract concept. For instance, when we feel tited, we might say we haven't any energy; and we read about the need to find alternatives t0 nonrenewable energy sources. Unlike matter, energy is known and recognized by its effects. It cannot be seen, touched, smelled, or weighed. Energy is usually defined as the capacity ro do work. In Chapter 5 we defined work as “force X distance,” but we will soon see that there are other kinds of work. All forms of energy are capable of doing work (that is, of exerting a force over a distance), but not ail of them are equally relevant to chemistry. The energy contained tidal waves, for example, can be harnessed to perform useful work, but the rela- tionship between tidal waves and chemistry is minimal. Chemists define work as directed energy change resulting from a process. Kinetic energy—the energy pro- duced by # moving object—is one form of energy that is of particular interest to chemists. Others include radiant energy, thermal energy, chemical energy, and poten- tial energy. Radiant energy, or solar energy, comes from the sun and is Earth's primary energy source, Solar energy heats the atmosphere and Earth’s surface, stimulates the ‘growth of vegetation through the process known as photosynthesis, and influences ‘global climate patterns Thermal energy is the energy associated with the random motion of atoms and ‘molecules. In general, thermal energy can be calculated from temperature measurements. ‘The more vigorous the motion of the atoms and molecules in a sample of matter, the hotter the sample is and the greater its thermal energy. However, we need to distinguish carefully between thermal energy and temperature. A cup of coffee at 70°C has a higher temperature than a bathtub filled with warm water at 40°C, but much more thermal ‘energy is stored in the bathtub water because it has a much larger volume and greater mass than the coffee and therefore more water molecules and more molecular motion. Chemical energy is stored within the structural units of chemical substances; its ‘quantity is determined by the type and arrangement of constituent atoms. When sub- stances participate in chemical reactions, chemical energy is released, stored, or con- verted to other forms of energy. Potential energy is energy available by virtue of an object's position. For instance, because of its altitude, a rock at the top of a cliff has more potential energy and will make a bigger splash if it falls into the water below than a similar rock located part- ‘way down the cliff. Chemical energy can be considered a form of potential energy because it is associated with the relative positions and arrangements of atoms within a given substance. lll forms of energy can be converted (at least in principle) from one form to another, We feel warm when we stand in sunlight because radiant energy is converted to thermal energy on our skin. When we exercise, chemical energy stored in our bodies is used to produce kinetic energy. When a ball starts to roll downhill, its potential energy is converted to kinetic energy. You can undoubtedly think of many other examples. Although energy can assume many different forms that are interconvertible, scientists have concluded that energy can be neither destroyed nor created. When one form of energy disappears, some other form of energy (of equal magnitude) must appear, and vice versa, This principle is sum- marized by the law of conservation of energy: the total quantity of energy in the universe is assumed constant, waa, ‘As the woter fats over the dam, = potent! energy is canverted to enaie energy. Use of is eneray to generate esecricy is cated yaroeiectic power232 Chapter 6 «Thermochemistry This red photo shows where energy nea) leaks through the Inouse. The more red the colt the more energy i lost fo the ousce sap Animation Energy Changes in Chemical Reactions ‘Often the energy changes that take place during chemical reactions are of as yiuch practical interest as the mass relationships we discussed in Chapter 3. For example, combustion reactions involving fuels such as natural gas and oil are carried out in Atily Tife more for the thermal energy they release than for their products, which are ‘water and carbon dioxide. ‘Almost all chemical reactions absorb or produce (release) energy, generally in the form of heat. It is important to understand the distinction between thermal energy and heat. Heat is the transfer of thermal energy between two bodies that are at dif- erent temperatures. Thus, we often speak of the “heat flow” from a hot object to a ‘cold one, Although the term “heat” by itself implies the transfer of energy, we cus- tomarily talk of “heat absorbed” or “heat released” when describing the eneray changes that occur during a process. Thermochemistry is the study of heat change in chemical reactions. To analyze energy changes associated with chemical reactions we must first define the system, or the specific part of the universe that is of interest to us. For chemists, systems usually include substances involved in chemical and physical changes. For «example, in an acid-base neutralization experiment, the system may be a beeker con- taining 50 mL of HCI to which 50 mL of NaOH is added. The surroundings are the rest of the universe ouside the system. ‘There are three types of systems. An open system can exchange mass and energy, usually in the form of heat with its surroundings. For example, an open system may consist of a quantity of water in an open container, as shown in Figure 6.1(@). If we lose the flask, asin Figure 6.1(b), so that no water vapor ean escape from or condense into the container, we create a closed system, which allows the transfer of energy (heat) but not mass. By placing the water in a totally insulated container, we can construct an isolated system, which does not allow the transfer of either mass or ‘energy, as shown in Figure 6.1(0). The combustion of bydrogen gas in oxygen is one of many chemical reactions that release considerable quantities of energy (Figure 6.2) 2H,(g) + Ox(g) —> 2H,0(0 + eneray In this case, we label the reacting mixture (hydrogen, oxygen, and water molecules) the system and the rest of the universe the surroundings. Because energy cannot be Water vapor i s 4 =U —) @ © © Figure 6.1 ree systems representa by water ma fask (on open system, which afows the ‘sehange of bath energy ond moss win sorourangs:b}@eosed sytem which alors he ‘renange of enerey but pet moss ond) an Soutea stm which atews node’ energy Dor ‘nosso be eenanged (ere the fests enclosed bya vecuum face).6.2 Energy Changes in Chemical Reactions 233 created or destroyed, any energy lost by the system must be gained by the sur- roundings. Thus, the heat generated by the combustion process is transferred from the system to its surroundings. This reaction is an example of an exothermic pro- cess, which is any process that gives off heat—that is, transfers thermal energy 10 the surroundings. Figure 6.3(a) shows the energy change for the combustion of hydrogen gas. ‘Now consider another reaction, the decomposition of mercury(Il) oxide (HgO) at high temperatures: energy + 2HgO(s) —> 2Hg() + Ox(g) ‘This reaction is an endothermic process, in which heat has to be supplied t0 the system (that is, to Hg0) by the surroundings (Figure 6.3(b)]. From Figure 6.3 you ean see that in exothermic reactions, the total energy of the products is less than the total energy of the reactants. The difference is the heat sup- plied by the system to the surroundings. Just the opposite happens in endothermic reactions, Here, the difference between the energy of the products and the energy of the reactants is equal to the heat supplied to the system by the surroundings. | 2te»+0x0 | | ae ox — Eade Rogier tare a bene yuan a tates a To the surroundings a ‘from the surroundings | aK | 2H) | @ O) Figure 6.2 The Hindenburg (On heating, HgO decomposes to give Hg and > Figure 6.3 fa)n exoiiermie process (2) An endothermic process. Ports (o) and (ore not van tothe some sea: ot heat released inte formation (OfH:0 fom, and Ozis not ‘equal to the hectabserbedin the Secompostion of gO.234 Chapter 6 = Thermochemistry Review of Concepts Classify cach of the following as an open system, a closed system, or an isolated system, (@) Milk kept in a closed thermo Mask. ()A stadent reading in her dorm room. (©) Air inside a tennis ball. Introduction to Thermodynamics ‘Thermochemistry is part of a broader subject called thermodynamics, which is the scientific study of the interconversion of heat and other kinds of energy. The laws of thermodynamics provide useful guidelines for understanding the energetics and direc~ tions of processes. In this section we will concentrate on the frst law of thermody- namics, which is particularly relevant to the study of thermochemistry. We will continue our discussion of thermodynamics in Chapter 17. In thermodynamics, we study changes in the state of @ system, which is defined by the values of alt relevant macroscopic properties, for example, composition, energy, temperature, pressure, and volume. Energy, pressure, volume, and temperature are said to be state functions—properties that are determined by the state of the system, regardless of how that condition was achieved. In other words, when the state of a system changes, the magnitude of change in any state function depends only on the Initial and final states of the system and not on how the change is accomplished, ‘The state of a given amount of a gas is specified by its volume, pressure, and temperature. Consider a gas at 2 atm, 300 K, and 1 L (Qe inital state). Suppose a process is carried out at Constant temperature such that the gas pressure decreases to 1 atm, According to Boyles law, its volume mast increase to 2 L. The final state then corresponds to I atm, 300 K, and 2 L. The change in volume (AV) is The Greckletar sot, Ssyrbotzes AV=Vi- My = 2L-1L SIL where V; and V; denote the initial and final volume, respectively. No matter how we arrive at the final state (for example, the pressure of the gas can be increased first and then decreased to 1 atm), the change in volume is always 1 L. Thus, the volume of a gas is a state function. In a similar manner, we can show that pressure and tem- perature are also state functions. Fecalatonobsetposeses potest Energy is another state function. Using potential energy as an example, we find Sieq/mveortepomeons'e=H| thatthe net increase in gravitational potential energy when we go from the sime copes starting point to the top of a mountain is always the same, regardless of how we get there (Figure 6.4), The First Law of Thermodynamics ‘The first law of thermodynamics, which is based on the law of conservation of energy, states that energy can be converted from one form to another, but cannot be created ‘or destroyed.’ How do we know this is so? It would be impossible to prove the valid- ity of the first law of thermodynamics if we had to determine the total energy content ‘See Toomoie on p. 40 (Chapter 2 fora discussion of nas and ener relationship in chemical reaeins63 Introduction to Thermodynamics 235 of the universe, Even determining the total energy content of 1 g of iron, say, would be extremely difficult. Fortunately, we can test the validity of the first law by measur- ing only the change in the internal energy of a system between its initial state and its {final state in a process. The change in internal energy AU is given by AU=U;-U, where U; and Ur are the internal energies of the system in the initial and final states, respectively. ‘The internal energy of a system has two components: kinetic energy and potential ‘energy, The kinetic energy component consists of various types of molecular motion and the movement of electrons within molecules. Potential energy is determined by the attractive interactions between electrons and nuclei and by repulsive interactions between electrons and between nuclei in individual molecules, as well as by interac- tion between molecules. It is impossible to measure all these contributions accurately, so We cannot calculate the total energy of a system with any certainty. Changes in energy, on the other hand, can be determined experimentally. Consider the reaction between 1 mole of sulfur and 1 mole of oxygen gas to produce 1 mole of sulfur dioxide: S(s) + Ox) — SO,(8) In this case, our system is composed of the reactant molecules $ and O; (the initial state) and the product molecules SO» (the final state). We do not know the internal ‘energy content of either the reactant molecules or the product molecules, but we can ‘accurately measure the change in energy content, AU, given by AU = U(product) — U(reactants) ‘energy content of 1 mol $Oa(g) ~ energy content of [1 mol S(s) +1 mol O:(g)] We find that this reaction gives off heat. Therefore, the energy of the product is less than that of the reactants, and AU is negative. Interpreting the release of heat in this reaction to mean that some of the chemical ‘energy contained in the molecules has been converted to thermal energy, we conclude that the transfer of energy from the system to the surroundings does not change the total energy of the universe, That is, the sum of the energy changes must be zero: MU, + AUsan = 0 ot MU yy = ~MUsue where the subscripts “sys” and “sur” denote system and surroundings, respectively. Thus, if one system undergoes an energy change AU, the rest of the universe, oF ure 6.4 The goin in ‘gravtationa potento! energy that ‘2ccurs when @ person climbs from the base tothe fop of ‘mountain is independent ofthe oth taken,236 Chapter 6« Thermochemistry the surroundings, must undergo a change in energy that is equal in magnitude but opposite in sign (—AUy,); energy gained in one place must have been lost somewhere clse. Furthermore, because energy can be changed from one form to another, the energy lost by one system can be gained by anather system in @ different form. For example, the energy lost by burning oil in & power plant may ultimately tum up in four homes as electrical energy, heat, light, and so on. In chemistry, we are normally interested in the energy changes associated with the system (which may be a flask containing reactants and products), not with its surroundings. Therefore, @ more useful form of the first law is Au=q+w on (We drop the subscript “sys” for simplicity.) Equation (6,1) says that the change in the internal energy, AU. of a system is the sum of the heat exchange q between the system and the surroundings and the work done w on (or by) the system. The sign conventions for g and w are as follows: q is positive for an endothermic provess and negative for an exothermic process and w is positive for work done on the system by the surroundings and negative for work done by the system on the surroundings. ‘We can think of the first law of thermodynamics as an energy balance sheet, much like a money balance sheet kept in a bank that does currency exchange. You can ‘withdraw or deposit money in either of (wo different currencies (like energy change due to heat exchange and work done). However, the value of your bank account depends only on the net amount of money left in it after these transactions, not on which currency you used. Equation (6.1) may seem abstract, but it is actually quite logical. If a system loses heat to the surroundings or does work on the surroundings, we would expect its internal energy to decrease because those are energy-depleting processes. For this, reason, both q and w are negative. Conversely, if heat is added to the system or if ‘work is done on the system, then the internal energy of the system would increase. In this case, both g and w are positive, Table 6.1 summarizes the sign conventions for q and Work and Heat We will now look at the nature of work and heat in more detail Work ° We have seen that work can be defined as foree F multiplied by distance werxd 62) In thermodynamics, work has a broader meaning that includes mechanical work (for example, a crane lifting @ steel beam), electrical work (a battery supplying electrons Table 6.1 Process Sign ‘Work done by the system on the surroundings = ‘Work done on the system by the surroundings + [Heat absorbed by the system from the surroundings (endothermic process) + ‘Heat absorbed by the surroundings from the system (exothermic process) _6.3 Introduction to Thermodynamics 23; av to light the bulb of a flashlight), and surface work (blowing up a soap bubble). In this section we will concentrate on mechanical work; in Chapter 18 we will discuss the nature of electrical work. (One way to illustrate mechanical work is to study the expansion or compression of a gas. Many chemical and biological processes involve gas volume changes. Breath- ing and exhaling air involves the expansion and contraction of the tiny sacs called alveoli in the lungs. Another example is the internal combustion engine of the aulo- mobile. The successive expansion and compression of the cylinders due to the com- bbustion of the gasoline-air mixture provide power to the vehicle. Figure 6.5 shows a gas in a cylinder Gited with a weightless, frictionless movable piston at a certain Temperature, pressure, and volume. As it expands, the gas pushes the piston upward against a constant opposing external atmospheric pressure P The work done by the ‘gas on the surroundings is PAV 3) here AV, the change in volume, i given by V; ~ Vj. The minus sign in Equation (6.3) takes care of the sign convention for w. For gas expansion (work done by the system), AV > 0, so ~PAV is a negative quantity. For gas compression (work done on the system), AV <0, and PAV is a positive quantity ‘Equation (6.3) derives from the fact that pressure X volume can be expressed as (Gorelarea) X volume; that is, PXV=—5 x @ =FXd=w Sl ese volome where F is the opposing force and d has the dimension of length, d* has the dimen- sions of area, and d° has the dimensions of volume, Thus, the product of pressure and volume is equal to force times distance, or work. You can see that fr a given increase in volume (that is, for a certain value of AV), the work done depends on the magni- tude of the extemal, opposing pressure P. If P is zero (tha is ifthe gas is expanding against a vacuum), the work done must sso be zero. If P is some postive, nonzero value, then the work done is given by ~PAV. "According to Equation (6.3), the units for work done by or on a a8 are liter atmospheres. To express the work done in the more familiar unit of joules, We use the conversion factor (see Appendix 2). TL + atm = 101.37 Figure 6.5 the expansion ofo (908 against o consiont externa! Bressure euch as atmospheric pressure} The gos no cylinder faved wit a woigniess movabie Bison. The work dane is give by PAV, Because al work done i a nego238 ‘Chapter 6+ Thermochemistry Sr eblams 65,696. Bscaue tempest kp onetan fol resueis te same na ond Example 6. A certain gas expands in volume from 2.0 L to 6.0 L at constant temperature. Calculate the work done by the gas if it expands (a) against a vacuum and (b) against a constant pressure of 1.2 atm Strategy A simple sketch of the situation is helpful here: Primi P > uitial "The work done in gas expansion is equal tothe product of the external, opposing pressure and the change in volume. What is the conversion factor between L.» atm and J? (a)Pz0 (b) Po | Radon Vz (6.0-20)L =40L Solution (@) Because the extemal pressure Is zero, no work is done in the expansion w= PAV, (0)(60~20)L =0 (©) The external, opposing pressure is 1.2 atm, s0 w= -PAV (1.2m)(60 ~ 2.0) L 481+ atm ‘To convert the answer to joules, we write = 49x 107 Check Because ths is gas expansion (work is done by the system on the surroundings), the work done has a negative sign. Practice Exercise A gas expands from 264 mL. to 971 mL at constant temperature. CCatealate the work done (in joules) by the gas if it expands (a) agoinst a vacuum and (©) against a constant pressure of 4.00 atm. ‘Example 6.1 shows that work is not a state function. Although the initial and final states are the same in (a) and (b), the amount of work done is different because the extemal, opposing pressures are different. We cannot write Aw = w; — w; for a cchange. Work done depends not only on the initial state and final state, but also on hhow the process is carried out, that is, on the path,63 Introduction to Thermodynamics 239 Heat ‘The other component of internal energy is heat, g. Like work, heat is nota state func- tion. For example, it takes 4184 J of energy to raise the temperature of 100 g of water from 20°C to 30°C. This energy can be gained (a) directly as heat energy from a Bunsen bumer, without doing any work on the water; (b) by doing work on the water without adding heat energy (for exemple, by string the water with a magnetic stir bar); or (c) by some combination of the procedures described in (2) and (b). This | simple illustration shows that heat associated witha given process, lke work, depends on how the process is carried out, It is important to note that regardless of which procedure is taken, the change in internal energy of the system, AU, depends on the sum of (q + w). Ifchanging the path from the initial state to the final state increases the value of q then it will decrease the value of w by the same amount and vice versa, so that AU remains unchanged. ‘Tn summary, heat and work are not state functions because they are not properties of a system, They manifest themselves only during a process (during a change). Thus, their values depend on the path of the process and vary accordingly. ‘The work done when a gas is compressed in cylinder like that shown in Figure 6.5 is 462 J, During this process, there is «eat transfer of 128 J from the gas tothe suroundings. CCaleulate the energy change for this process. Strategy Compression is work done on the gas, so what isthe sign for w? Heat is released by the gas to the surroundings. Is this an endothermic or exothermic process? ‘What isthe sign for? Solution ‘To caleulte the energy change ofthe gas, we need Equation (6.1). Work of ‘compression is positive and bocause heat is released by the gas, q i negative. Therefore, we have AU=q+w 1281 + 4621 = 3MJ ‘As a result, the energy of the gas increases by 334 J ‘Sitar problems: 617 618. Practice Bxercive A gas expands and does P-V work on the surroundings equal to 279 J. At the same time, it absorbs 216 J of heat from the surroundings. What is the change in energy of the system? Review of Concepts ‘Two ideal gases at the same temperature and pressure are placed in two equal- volume containers. One container has a fixed volume, while the other is a cylinder fitted with a weightless movable piston like that shown in Figure 6.5 ‘tially, the gas pressures are equal tothe extemal atmospheric pressure. The gases are then heated with a Bunsen burner. What are the signs of q and w for the gases under these conditions?any phenomena in everyday life can be explained by the [first law of thermodynamics. Here we will discuss two examples of interest 10 lovers ofthe outdoors. ‘Making Snow Ifyou are an avid downhill skier, you have probably skied on atificial snow. How i this staff made in quantities large enough to meet the needs of skiers on snowless days? The socret of snowmaking is in the equation AU'= g++ w. A snowmaking ‘machine contains a mixture of compressed ir and water vapor at about 20 atm. Because ofthe large difference in pressure be- teen the tank and the ouside atmosphere, when the mi sprayed into the atmosphere it expands so rapidly that, as a good upproximation, no heat exchange occurs between the system (air and water) and its surroundings; that is, 9 = 0. (In thermo- ‘dynamics, uch a process is called an adiabatic process) Thos, we write AU=q+w=w ‘Because the system does work on the surroundings, wis 3 nega- tive quantity, and there isa decrease inthe system's energy. Kinetic energy is part of the total energy of the system. In ‘Section 5.7 we saw that the average kinetic energy of a gas is rectly proportional to the absolute temperature [Equation (5.15). It follows, therefore, thatthe change in energy AU is siven by Au=car ‘where Cis the proportionality constant, Because AU is nega- tive, AT must also be negative, and itis this cooling effect (or the decrease in the Kinetic energy of the water molecules) that is responsible for the formation of snow. Although we ‘need only water to form snow, the presence of air, which also Making Snow and Inflating a Bicycle Tire cools on expansion, helps to lower the temperature of the ‘water vapor. Inflating a Bicycle Tire If you have ever pumped air into a bicycle tie, you probably noticed a warming effect atthe valve stem. This phenome- ‘non, to, can be explained by the first law of thermodyaam- jes. The action of the pump compresses the air inside the pump and the tre. The process is rapid enough to be treated as approximately adiabatic, so that ¢ = 0 and AU = w. Because work is done on the gas in this case (it is being com= pressed), w is postive, and there is an increase in energy. Hence, te temperature ofthe system increases also, accord ing tothe equation au= car enthalpy of Chemical Reactions ‘Our next step is to see how the first law of thermodynamics can be applied to pro- ‘cesses cartied out under different conditions. Specifically, we will consider two situ- ations most commonly encountered in the laboratory; one in which the volume of the system is kept constant and one in which the pressure applied on the system is kept constant. 2406.4 Enthalpy of Chemical Reactions If chemical reaction is run at constant volume, then AV = 0 and no P-V work ‘will result from this change. From Equation (6.1) it follows that Au=q~ PAV =a (64) We add the subscript “W" to remind us that this is a constant-volume process. This equality may seem strange at first, for we showed earlier that q is not a state function. ‘The process is carried out under constant-volume conditions, however, so that the heat change can have only a specific value, which is equal to AU. Enthalpy Constant-volume conditions are often inconvenient and sometimes impossible to achieve, Most reactions occur under conditions of constant pressure (usually atmo- spheric pressure). If such a reaction results in a net increase in the number of moles ‘of a gas, then the system does work on the surroundings (expansion). This result follows from the fact that for the gas formed to enter the atmosphere, it must push the surrounding air back. Conversely, if more gas molecules are consumed than are produced, work is done on the system by the surroundings (compression). Finally, no ‘work is done if there is no net change in the number of moles of gases from reactants {0 products, Tn general, for a constant-pressure process we write Au=q+w % ~ PAV AU + PAV 63) or % Where the subscript “p” denotes constant-pressure condition. ‘We now introduce a new thermodynamic function of a system called enthalpy (11), which is defined by the equation H=U+PV (66) ‘where Us the internal energy of the system and P and V are the pressure and volume of the system, respectively. Because U and PV have energy units, enthalpy also has ‘energy units. Furthermore, U, P, and V are all state functions, that is, the changes in (U + PV) depend only on the initial and final states. It follows, therefore, that the change in H, or AH, also depends only on the initial and final states. Thus, Hf is a state function. For any process, the change in enthalpy according to Equation (6.6) is given by AH = AU + APY) 67) If the pressure is held constant, then AH= AU + PAV (68) Comparing Equation (6,8) with Equation (6.5), we see that for a constant-pressure process, qy = AH. Again, although q is not a state function, the heat change at constant pressure is equal to AH because the “path” is defined and therefore it can have only a specific value. 241242 Chapter 6» Thermochemistry etn omt ne subset a" ana “rope tor ntaipyenangor ct Bisby mead Fer sinotly, we se “et mol” rater We now have two quantities AU and AHthat can be associated with a reaction If the reaction occurs under constant-volume conditions, then the heat change, 4, is equal to AU. On the other hand, when the reaction is carried out at constant pressure, the heat change, g,, is equal to AH. Enthalpy of Reactions Because most reactions are constant-pressure processes, We can equate the heat change in these cases to the change in enthalpy. For any reaction of the type reactants —> products wwe define the change in enthalpy, called the enthalpy of reaction, AH xm a8 the difference between the enthalpies of the products and the enthalpies of the reactants: AH = H(produets) — H(reactants) (69) ‘The enthalpy of reaction can be positive or negative, depending on the process For an endothermic process (heat absorbed by the system from the surroundings), AH is positive (that is, AFV > 0). For an exothermic process (heat released by the system to the surroundings), A/T is negative (that is, AH <0). ‘An analogy for enthalpy change is a change in the balance in your bank account, ‘Suppose your initial balance is $100. After a transaction (deposit or withdrawal), the change in your bank balance, AX, is given by AX = Xfnat ~ Xi ‘where X represents the bank balance. IF you deposit $80 into your account, then AX = $180 ~ $100 = $80. This comesponds to an endothermic reaction. (The balance increases and so does the enthalpy of the system.) On the other hand, a withdrawal of $60 means AX = $40 ~ $100 = -S60. The negative sign of AX means your balance has decreased, Similarly, a negative value of AH reflects a decrease in enthalpy of the system as «result of an exothermic process. The diflerence between this analogy and Equation (6.9) is that while you always know your exact bank balance, there is no way to know the enthalpies of individual products and reactants. In practice, we can only measure the difference in their values. "Now let us apply the idea of enthalpy changes to two common processes, the first involving a physical change, the second a chemical change. Thermochemical Equations ALO°C and a pressure of 1 atm, ice melts to form liguid water. Measurements show that for every mole of ice converted to liquid water under these conditions, 601 Kilojoules (kof heat energy are absorbed by the system (ee). Because the pressure is constant, the heat change is equal to the enthalpy change, AH. Further more, this is an endothermic process, as expected for the energy-absorbing change of melting ice (Figure 6.6(a)], Therefore, A/T is « positive quantity. The equation for this physical change is H,0(s) —> H,0() AH = 6.01 ki/mol ‘The “per mole” in the unit for AFT means that this is the enthalpy change per mole of the reaction (or process) as itis writien; that is, when | mole of ice is converted 10 1 mole of liquid water.64 Enthalpy of Chemical Reactions 243 HO | CHA) + 20,00) Hea absorbed bythe system from the siroundings [a= 601K Enhalpy Entlpy 1100) cosa) + 24,000 @ [As another example, consider the combustion of methane (CH,), the principal component of natural gas: CHA(g) + 203(g) —> COx(g) + 2H,0() AH = ~890.4 ki/mol From experience we know that burning natural gas releases heat tothe surroundings, 0 itis an exothermic process. Under constant-pressure condition this heat change is equal to enthalpy change and AH must have a negative sign [Figure 6.6(b)). Again, the per mole of reaction unit for AH means that when 1 mole of CH, reacts with 2 moles of Oto produce 1 mole of COs and 2 moles of liquid H;0, 890.4 KI of heat nergy ate released to the surroundings. It is important to keep in mind thatthe AA value does not refer toa particular reaetunt or produet. It simply means thatthe quoted ‘BHT value refers to all the reacting species in molar quantities. Thus, the following ‘conversion factors can be created: 804K) -8904k 804K 890.4 KT ImolCH, 2molO; — TmolCO, — 2 mol HO Expressing AH in units of Ki/mol (rather than just KJ) conforms to the standard con- vention; its merit will become apparent when we continue our study of thermodynam- ies in Chapter 17, ‘The equations for the melting of ice and the combustion of methane are examples of thermochemical equations, which show the enthalpy changes as well as the mass relationships, Icis essential o specify a balanced equation when quoting the enthalpy change of a reaction, The following guidelines are helpful in writing and interpreting thermochemical equations. |. When writing thermochemical equations, we must always specify the physical states of all reactants and products, because they help determine the actual enthalpy changes, For example, in the equation for the combustion of methane, if we show water vapor rather than liguid water as a product, CHi(g) + 20;(¢) —> COx(a) + 2H,0(g) AH = —802.4 KK/mol the enthalpy change is -802.4 KJ rather than —890.4 KJ because 88,0 ky are needed to convert 2 moles of liquid water to water vapor; that is, 2H,0(!) —> 2H,0(g) AH = 88,0 k3/mol Figure 6.6 (4 Mettng mote ‘ce ot °C fan encotermic process resus in an enthooy Increase inthe system of BOT kL (0) Buraing I mote of methane In oxygen gas fan exotic process) resus nan entrolby ‘decrease nthe systom of 850-4 ks. Farts (¢) ar (3) are no drawn to the some seae. Methane gos burning tom 0 Bunsen bomer14 Chapter 6 » Thermochemistry (enaeed or aseeais oops ‘aly. The words “rewese 2. If we multiply both sides of a thermochemical equation by a factor n, then AH must also change by the same factor, Returning to the melting of ice H,0(s) —> H,0() AH= 01 kV/mol If we multiply the equation throughout by 2; that is, if we set m = 2, then 2H,0(s) —> 2H,0() AH = 2(6.01 ki/mol) = 12.0 ki/mol 3. When we reverse an equation, we change the roles of reactants and products Consequently, the magnitude of AH for the equation remains the same, but its sign changes. For example, if @ reaction consumes thermal energy from its surroundings (that is, if it is endothermic), then the reverse reaction must release thermal energy back to its surroundings (that is, it must be exothermic) and the enthalpy change expression must also change its sign, Thus, reversing the melting of ice and the combustion of methane, the thermochemical equa- tions become H.0() — 1,065) AH = 601 ki/mol COn(g) + 2H,0() —> CH(g) + 20;(¢) AH = 890.4 ki/mol ‘and what was an endothermic process becomes exothermic, and vice versa. Secs Given the thermochemical equation 250,(8) + Ox(e) —> 280\(@) AH = ~198.2k4/mo calculate the heat evolved when $7.9 g of SO, (molar mass = 64.07 gnol) i converted 10 805 Strategy "he thermochemical equation shows that for every 2 moles of SO; reacted, 198.2 Kd of heat are given off (note the negative sign). Therefore, the conversion factor is 198.240 mol SO; How many moles of SO> are in 879 ¢ of $O;? What is the conversion factor between grams and moles? Solution We need to first calculate the number of moles of SO» in 87.9 g of the ‘compound and then find the number of kilojoules produced from the exothermic reaction, The sequence of conversions is as follows: grams of SO; —> moles of $0; —> kilojoules of heat generated ‘Therefore, the enthalpy change for this reaction is given by Lok 805-1982) _ 64.07 g80; ” 2mo!SO; ~ AH = 87.9380; x and the heat released to the surroundings is 136 WJ. (Continued)6.4 Enthalpy of Chemical Reactions 245 Check Because 879 g is less than twice the molar mass of SO; (2 X 64.07 g) as shown in the preceding thermochemical equation, we expect the heat released to be smaller than 198.2 W. Practice Exercise Calculate the heat evolved when 266 g of white phosphorus (P,) bums in air according tothe equation P((s) + 50g) —> PiOy(s) AH = ~3013 kd/mot A Comparison of AH and AU What is the relationship between AH and AU for a process? To find out, fet us consider the reaction between sodium metal and water: 2Na(s) + 2H,0(l) —> 2NaOH(aq) + Hy(g) AH = ~367.5 ki/mol ‘This thermochemical equation says that when two moles of sodium react with an excess of water, 367.5 KI of heat are given off. Note that one of the products is hydrogen gas, which must push back air to enter the atmosphere. Consequently, some of the energy produced by the reaction is used to do work of pushing back @ volume of air (AV) against atmospheric pressure (P) (Figure 6.7). To calculate the change in internal energy, we rearrange Equation (6.8) as follows: AU = AH- PAV If we assume the temperature to be 25°C and ignore the small change in the volume of the solution, we can show thal the volume of | mole of H; gas at 1.0 atm and 298 K is 24.5 L, so that PAV = ~24.5 L + atm or ~2.5 KI. Finally, AU = ~367.5 kI/mol — 2.5 kI/mol 370.0 ki/mol Tris calculation shows that AU and AH are approximately the same. The reason AFT is smaller than AU in magnitude is that some of the internal energy released is used to do gas expansion work, so less heat is evolved. For reactions that do not involve gases, AV is usually very small and so AU is practically the same as AH. Another way to caleulate the internal energy change of a gaseous reaction is to assume ideal gas behavior and constant temperature. In this c AU =An- AV) HH — RTAn 6.10) Seat reacting with water fo Form hycrogen gas. ‘rom eacarts to rds fr orp, Hig) a) ane a= am Figure 6.7 (o)A neater of ctr inside 0 cynder fitted with ‘@movable ston. The pressure Inside equa tothe otmospneric pressure.) As the sodium ‘mete! reacts with were the >nytrogen gos generetcd pushes the piston upward (or ‘on the suroundings) pressure inside is again equol to thot of outst246 Chapter 6 Thermochemistry ¢ ee | carbon menaxide burns na to orm carbon dioxide. Sire prolen: 6.2% where An is defined as ‘An = number of moles of product gases ~ number of moles of reactant gases Ee CCateulate the change in intemal energy when 2 moles of CO are converted to 2 moles (of CO at 1 aim and 25°C: 2CO(s) + Ox(2) —> 2C0,{@) AH = 566.0 mot Strategy We are given the enthalpy change, AH, forthe reaction and sre asked t0 Calculate the change in internal energy, AU. Therefore, we need Equation (6.10). What is the change in the number of moles of gases? AH is given in kilojoules, so what units should wo use for R? Solution From the chemical equation we see that 3 moles of gases ure converted 10 2 moles of gases so that An = number of moles of product gas ~ number of moles of reactant gases 2-3 Using 8.314 /K + mol for R and T = 298 K in Equation (6.10), we write AU =AH~ RTAn = eco — ser m Be Jess mn = =563.5 ki/mol Check Knowing thatthe reacting gaseous system undergoes a compression (3 moles to 2 moles), is it reasonable to have A/T > AU in magnitude? Practice Exercise What is MU for the formation of 1 mole of CO at 1 atm and 25°C? C(graphite) + 10x(g) —> COs) AH = 110.5 Ki/mol Review of Concepts Which of the constant-pressure processes shown here has the smallest difference ‘between AU and AH? (@) water —> water vapor (b) water — ice (©) ice —> water vapor & calorimetry In the laboratory, heat changes in physical and chemical processes are measured with ‘a calorimeter, a closed container designed specifically for this purpose. Our discussion of calorimetry, the measurement of heat changes, will depend on an understanding of specific heat and heat capacity, so let us consider them first Specific Heat and Heat Capacity ‘The specific heat (5) of a substance is the amount of heat required to raise the temperature of one gram of the substance by one degree Celsius. It has the units Ug = °C. The heat capacity (C) of a substance is the amount of heat required 10raise the temperature of a given quantity of the substance by one degree Celsius Its units are °C. Specific heat is an intensive property, whereas heat capacity is an extensive property. The relationship between the heat capacity and specific heat of a substance is C= ms al) where mis the mass of the substance in grams. For example, the specific heat of water is 4.184 J/g + °C, and the heat capacity of 60.0 g of water is (60.0 g)(4.184 Ig» °C) = 251°C ‘Table 6.2 shows the specific heat of some common substances. If we know the specific heat and the amount of a substance, then the change in the sample’s temperature (A1) will tell us the amount of heat (q) that has been absorbed of released in a particular process. The equations for calculating the heat change are given by q = msat (6.2) q= Chr (6.13) where At is the temperature change: t= tot — ‘The sign convention for q is the same as that for enthalpy change; q is positive for endothermic processes and negative for exothermic processes. A 466-g sample of water is heated from 8.50°C to 74.60°C. Calculate the amount of ‘heat absorbed (in kilojoules) by the water. We know the quantity of water and the specific hest of water. With information and the temperature rise, we can calculate the amount of heat absorbed (a). sing Equation (6.12), we write = meat = (466 g)(4.184.g + °C)(74.60°C — 850°C) Lig 129 x 1081 x Solution = 129 Check The units g and °C cancel, and we are left with the desired unit ki. Because heat is absorbed by the water from the surroundings, it has a positive sign Practice Exercise An iron bar of mass 869 g cools from 94°C fo 5°C. Calculate the heat released (in kilojoules) by the metal. Constant-Volume Calorimetry Heat of combustion is usually measured by placing a known mass of « compound in 4 steel container called a constant-volume bomb calorimeter, which is filled with oxygen at about 30 atm of pressure, The closed bomb is immersed in a known amount 65 Calorimetry 27 | en ‘The Specific Heats, ‘of Some Common ‘Substances Specific Heat Substance —_(W/g + °C) Al 0.900 Au 0.129 C Graphite) 0-720 CG@iamond) 0.502 cu 0385, Fe 044 He 0.139 Pb 0138 #0 4.184 CxHLOH (ethanol) 2.46 ‘ioe notre fhe eocton on Simoes proves of cess248 Chapter 6 » Thermochemistry Figure 6.8 4 constontvotume ‘bomb colorimeter The colormeter '5 files win oxygen gos before itis placedin the bucket The sompie ignited electrcoty, ond the neat produced by the reaction can be accurately determined bby measuring tne temperature Increase in the known amount of surrounaing water of water, as shown in Figure 6,8. The sample is ignited electcally, and the heat produced by the combustion reaction can be calculated accurately by recording the rise in temperature of the water. The heat given off by the sample is absorbed by the ‘water and the bomb. The special design of the calorimeter enables us to assume that no heat (or mas) is lost to the suroundings during the time it takes to make measure- ‘ments. Therefore, we can call the bomb and the water in which itis submerged an isolated system. Because no heat enters or eaves the system throughout the process, the heat change of the system (Gaya) must be 2270 and we can write Geyser = Gest + Ges =0 (aa) ‘where gay and diay are the heat changes for the calorimeter and the reaction, respec- tively. Thus, Gen = ~ esi (6.15) Noteshatcacomprsesbomnevonb To calculate qeuy we need to know the heat capacity of the calorimeter (Cay) and the ewe srrsnarg wate temperature rise. tht is. Gea = Coyt (6.16) ‘The quantity Ca, is calibrated by burning a substance with an accurately known heat of combustion. For example, it is known that the combustion of 1 g of benzoic acid (CdH,COOH) releases 26.42 KI of heat. Ifthe temperature rise is 4.673°C, then the heat capacity of the calorimeter is given by soap remertitone ition ar ciibaraome 262s = 46°C 5.654 KPC ‘Once Ca has been determined, the calorimeter can be used to measure the heat of ‘combustion of other substances. Note that because reactions in a bomb calorimeter occur under constant- volume rather than constant-pressure conditions, the heat changes correspond to AU,6.5 Calorimetry 249 not the enthalpy change AH (see Section 6.4). Equation (6.10) can be used to correct the measured heat changes so that they correspond to AH values, but the corrections usually are quite small so we will not concern ourselves with the details hhere. Finally, it is interesting to note that the energy contents of food and fuel (usually expressed in calories where 1 cal = 4.184 J) are measured with constant- volume calorimeters Em ° ‘A quantity of 1435 g of naphthalene (CoH), a pungent-smeling substance used in ‘moth replloms, was burned in a constant-volume bomb calorimeter. Consequently, the temperature of the water rose from 20.28°C to 25.95°C. If the heat capacity of the bomb plus water was 10.17 KIFC, calculate the heat of combustion of saphthalene on 4 molar basis; that, find the molar heat of combustion. ee e®@ @c ee ee@ Oc e Sirategy Knowing the beat capacity and the temperature rise, how do we calculate the het absorbed by the calorimeter? What is the heat generated by the combustion of 1435 g of naphthalene? What is the conversion factor between grams and moles of ‘naphthalene? Solution The heat absorbed by the bomb and water is equal to the product of the heat capacity and the temperature change. From Equation (6.16), assuming no beat is lost to the surroundings, we write Culig a1 = Casdt = 0.17 KIC) (25.95°C ~ 20.28°C) = 57.66 KI Becase gon = det + don ~ 0; at = ~@uw The heat chang of th econ is ~57.6 i. This is heat clened bythe combustion of 1485 g of Gil terefore we can wie the conversion factor =S2868_ 1485 Cult ‘he molar mis of naphalene is 1282 gs the heat of combustion of 1 moe of naphthalene is OOK, 1282 Cable 1435 g.Cobig ” 1 mol Cyl 4151 x 10" ki/mol ‘molar heat of combustion = (Check Knowing thatthe combustion reaction is exothermic and that the molar mass of, ‘naphthalene is much greater than 1.4 g, is the answer reasonsble? Under the reaction conditions, can the heat change (57.66 kJ) be equated to the enthalpy change of the reaction? Sir poses 637 Practice Exercise A quantity of 1.922 of methanol (CH,OH) was bumed in a constant-volume bomb calorimeter. Consequently, the temperature of the water rose by 420°C. Ifthe heat capacity of the bomb plus water was 10.4 KIC, calculate the molar beat of combustion of methanol Constant-Pressure Calorimetry ‘A simpler device than the constant-volume calorimeter is the constant-pressure calo- rimeter, which is used to determine the heat changes for noncombustion reactions. A ‘crude constant-pressure calorimeter can be constructed from two Styrofoam coffeeWhite Fat Cells, Brown Fat Cells, and a Potential Cure for Obesity ae food we eat is broken down, or metabolized, in stages by a group of complex biological molecules called en- zymes. Most of the energy released at each stage is captured for function and growth. One interesting aspect of metabolism is that the overall change in energy isthe same as itis in com- ‘bustion. For example, the total enthalpy change forthe conver- sion of glucose (CyH:0,) to carbon dioxide and water is the same whether we burn the substance in air or digest it in ‘oar bodies CyHiOu(s) + 6CONg) —+ 6CO.(g) + 6H,0€) AH = ~2801 Ki/mol “The energy content of food is generally measured in caries. The «calorie (cals a now Stunt of enesgy that is equivalent 04.184 Leal = 4.1845 In the context of nutrition, however, the calorie we speak of (sometimes called a "big calorie”) is actualy equal toa kilo- calorie; that is, ‘The bomb calorimeter described in Section 6.5 is for measuring the energy content, or “fuel values.” of foods (see table), ‘The excess energy from food is stored inthe body in the form of fats, Fats are a group of organic compounds (testers of glycerol and fatty acids) that are soluble in organic sol- vents but insoluble in water. There are two types of fat cells called the white fat cells (WEC) and brown fat cells (BFC). ‘The WFC are designed to store energy for use in time of need for body function. They accumulate under the skin and around Fuel Values of Foods Substance AH anasion KE) Apple -2 Milk -3 Potatoes 3 rerperore 250 internal organs and they cushion and insulate the body. Obese people have a high content of WFC in their bodies. BFC, on the other hand, contain a high concentration of mitochondria, which ae specialized subunits within a cell, The main role of BEC is to bum fat molecules and generate heat. Its name is derived from the fact that mitochondria conten iron, giving the tissue a reddish brown color. In general, women have ‘more BFC than men, ‘We lose our brown fat as we age, but several studies carried fut in 2009 showed that adults possess metabolically active BBFC. la one expesiment, PETICT (positron emission tomogra- phy and computerized tomography) scans of 24 men exposed to cold and room temperature show thatthe chilly temperature sotivates the BEC as they burn off ft molecules to generate heat (see figure). Furthermore, it was found that lean people have more setive BFC than obese people. ‘Mice have the same type of fat cells as humans. In 2013 it was demonstrated by genetically labeling the fat cells of mice that WFC could he converted into BFC by exposure to cold (°C) for one week. Unfortunately, BFC were converted back to WEC a few woeks after the mice were returned to normal room temperature. A separate study suggested that a different type of [BFC ean be Formed from WFC by exercise Obesity is a major health hazard in the United States. “Treatments for obesity so far are focused on diet to lower the amount of energy consumed, or exercise to increase the amount of energy the body needs. Most current antiobesity NaCl(aq) + HOW) 562 Heat of ionization H40() —> H*(aq) + OH™(aq) 562 Heat of fusion H,0(s) —+ 1,00) 601 “Heat of vaporization H0() —> H,0(8) 440 Heat of reaction MgCL(s) + 2Na() —> 2NaCl(s) + Ma(s)—— ~1802 ‘Meanced 325. At 10 the wa is 4:79 cups, as shown in Figure 6.9, This device measures the heat effects of a variety of reactions, such as acid-base neutralization, as well as the heat of solution and heat of dilution. Because the pressure is constant, the heat change for the process (dna) is ‘equal to the enthalpy change (AH). As in the case of a constant-volume calorimeter, \we treat the calorimeter as an isolated system. Furthermore, we neglect the small heat capacity of the coffee cups in our calculations. Table 6.3 lists some reactions that have been studied with the constant-pressure calorimeter. Ske A lead (Pb) pellet having a mass of 26.47 g at 89.98°C was placed in @ constant-pressure calorimeter of negligible heat capacity containing 100.0 mL of water. The water temperature rose from 22.50°C to 23.17°C. What is the specifi heat ofthe lead pellet? Strategy A sketch of the inital and final situation is as follows: Dritiok_ Pb-@ 2479 + Osan 7205 Feb BBIT% @ ‘We know the masses of water and the Jead pellet as well as the initial and final ‘temperatures. Assuming no heat is lost to the surroundings, we can equate the heat lost by the lead pellet to the heat gained by the water. Knowing the specific heat of water, we can then calculate the specific heat of lead Solution Trestng the calorimeter as an isolated system (no heat lst to the surroundings), wwe write nade am + Quo = or Gm =~ a0 ‘The heat gained by the water is given by ano = msde (Continued) 251 65 Calorimetry Temonet I Styrofoam cups Stier Rescian Figure 6.9 4 constant pressure calorimeter mode oF to. ‘Syroteum coffee cups. The outer ‘up helps to insulate the reacting ture fom the surounings Tao soutions af nov volume containing te reactants ot he same lomperature are carefully ‘nied i the colonmeter The neat proouced or obsorbed by Ihe reoction can be determined ‘by measunng the temperature change252 (Chapter 6» Thermochemistry Sir problem: 6.8, Sir problen: 638 where m and s are the mass and specific heat and At = fs ‘go = (100.0 g)(4.184 Hg + *C)(23.17°C ~ 250°C) = 2803 ‘Because the heat lost by the lead pellet is equal to the heat gained by the water, ‘ans = ~280.3 J, Solving for the specific heat of Pb, we write nm = mst =280.3 3 = (26.47 g)(s)(23.17°C ~ $9.98°C) = O18 Ie °C Practice Exercise A 30.14g stainless steel ball bearing at 117.82°C is placed in a constan-pressure calorimeter containing 120.0 mL of water at 1844°C. Ifthe specific Iheat of the ball bearing is 0.474 Ig + °C, calculate the final temperature of the water. Assume the calorimeter (o have negligible heat capacity. ‘A quamity of 1.00 % 10? mi of 0500 Mf HCL was mined wit 1.00 > 10% mL of 0.500 AF [NaOH in constuntpessiecalrimeer of nelgble eat caps. The nia temperate of the HCI and NaOH solutions was the same, 225°C, and te final temperature ofthe nixed solution was 25.86. Calcalate the het change forthe neutalizaton reaction on & role best NaOH(ag) + HCK(ag) —+ NaCl(ag) + 1,00) ‘Assume thatthe densities and specific heats ofthe solutions are the same as for water (1.00 g/mL. and 4.184 Sig + °C, respectively). Strategy Because the temperstre rose, the neutralization reaction is exothermic. How do ‘we calculate the heat absorbed by the combined solution? What is the beat of the reaction? ‘What is the conversion factor for expressing the heat of rection on a molar basis? Solution Assuming no heat is 1st 1 the suroundings, dn = dune + dae = 0,50 rn = Gum Wh diy is the heat absorbed by the combined solution. Because the density ofthe solution is 1.00 gin, the mass ofa 100-ml. solution is 100 g. Thus, dun = mht = (1.00 x 10" g + 1.00 x 10 g) (4.184, + °C)(25.86°C ~ 22.50°C) = 281 x 10°F = 281K) Because dus = Auten dre = ~2.81 rom dhe moasities given, the number of moles of both HCL and NeOH in 1.00 % 10* mi solution is 10,0500 mot ‘Therefore, the heat of neutralization when 1.00 mole of HCI reacts with 1,00 mole of NaOH is 2818 heat of neutralization = 55 ey 36.2 ki/mol Check 1s the sign consistent with the nature of the reaction? Under the resction condition, can the heat change be equated tothe enthalpy change? Practice Exercise A quantity of 4.00 x 10° mL of 0.600 M HNO, is mixed with 4400 X10 mL of 0300 af Bx(OH), in constanpressre calorimeter of neligile heat capacity. The inal emeratre of both solutions ste sare a 184°C. What isthe final temperature ofthe solution? (Use te esl in Example 68 for your calultion6.6 Standard Enthalpy of Formation and Reaction Review of Concepts A 1g sample of Al and a I-g sample of Fe are heated from 40°C to 100°C, Which metal has absorbed a greater amount of heat? GB Standard Enthalpy of Formation and Reaction So far we have learned that we can determine the enthalpy change that accompanies a reaction by measuring the heat absorbed or released (at constant pressure). From [Equation (6.9) we see that AH can also be calculated if we know the actual enthalpies of all reactants and products. However, as mentioned earlier, there is no way fo measure the absolute value of the enthalpy of a substance. Only values relative to an arbitrary reference can be determined. This problem is similar to the one geographers face in expressing the elevations of specific mountains or valleys. Rather than trying to devise some type of “absolute” elevation scale (perhaps based on distance from the center of Earth), by common agreement all geographic heights and depths are expressed relative to sea level, an arbitrary reference with a defined elevation of “zero” meters or feet. Similarly, chemists have agreed on an arbitrary reference point for enthalpy. ‘The ‘sea level” reference point for all enthalpy expressions is called the standard ‘enthalpy of formation (SH). Substances are said to be in the standard state at 1 atm,” hence the term ‘standard enthalpy.” The superscript “*” represents standard-state con- ditions (1 atm), and the subscript“ stands for formation, By convention, the standard ‘enthalpy of formation of any element in its most stable form is zero. Take the element ‘oxygen as an example. Molecular oxygen (O;) is more stable than the other allotropic form of oxygen, ozone (Qs), at 1 atm and 25°C, Thus, we can write AH7(O;) = 0, but ‘AHj(O,) = 142.2 kJ/mol. Similarly, graphite is a more stable allotropic form of carbon than diamond at 1 atm and 25°C, so we have AHM(C, graphite) = 0 and AHAC, diamond) = 1.90 k¥/mol. Based on ths reference for elements, we can now define the standard enthalpy of formation of a compound as the heat change that results when I mole of the compound is formed from its elements at a pressure of 1 atm. Table 64 lists the standard enthalpies of formation for a number of elements and compounds. (For a more complete list of AH? values, see Appendix 3.) Note that although the standard state does not specify a temperature, we will always use AH? values measured at 25°C for our discussion because most of the thermodynamic data are collected at this temperature Review of Concepts Which of the following does not have AH = 0 at 25°C? No(g) Cu(s) Kr(g) Hg(s) Ha(s) Ls) ‘The importance of the standard enthalpies of formation is that once we know their values, we can readily calculate the standard enthalpy of reaction, AH, defined as she enthalpy of a reaction carried out at J atm, For example, consider the hypothetical reaction aA +B —> oC +aD where a, b, ¢ and d are stoichiometric coefficients. For this reaction, Affzy is given by [cAHR(C) + dAHH(D)] — [aAHH(A) + BAHAB)] — (6.17) AF, “In thermodynamics, the standard pressure is defined a I but, wher bar ~ 10 Pa ~ 0.987 atm, Because hr fers frm 1 atm by oly 1-3 percent, we will coninue owse | am asthe standard pressure, Note ‘atthe norm meking polt and bolling pot ofa substance ar defied jn terms of | th Groptite top) ond ciomond (otom, 253,254 Chapter 6 » Thermochemistry Standard Enthalpies of Formation of Some inorganic z Substances at 25°C 7 ee Substance AHks/enol) Substance AMF(kes/mo) Ast) 0 0-0) 1876 Agcls) =2210 A) o Als) 0 40) ° ALLOW) 1669.8 HI) 259) Br) ° Mgt) © Brg) 362 gos) -O18 (graphite) ° Mg0O,) -11129 (diamond) 1.90 Nw 0 cow) 105 NH) 463 Coxe) 393.5 Nova) 904 ca) 0 NOx) 3385 ca01) 635.6 N.0() 81.56 CaCO\(5) —12069 N04) 9.66 cua) 0 0) 209.8 Cis) 3823, O48) oO cu) 0 Oya) 102.2. cv) 1552 S(chombie) 0 F@) 0 ‘S(monoctinic) 030 HF) 2716 SOx) 296.1 H@) 2182 0g) 395.2 HA) 0 Si) 20.15 1.0%) 2418 2008) ° #00) 2858 Zn0(9) 348.0 We can generalize Equation (6.17) as HY, = ZnAH(products) — EmAHP(reactants) (6.18) where m and n denote the stoichiometric coefficients for the reactants and products, and (sigma) means “the sum of” Note that in calculations, the stoichiometric coef ficients are just numbers without units. ‘To use Equation (6.18) to calculate Aff,., we must know the AH? values of the compounds that take part in the reaction. These values can be determined by applying the direct method or the indireet method. The Direct Method ‘This method of measuring AH works for compounds that can be readily synthesized from their elements. Suppose we want to know the enthalpy of formation of carbon dioxide. ‘We must measure the enthalpy of the reaction wien carbon (graphite) and molecular ‘oxygen in thei standard states are converted to carbon dioxide in its standard state: C(graphite) + Ox(g) —> CO,(g) AHjay = ~393.5 kl/mol We know from experience that this combustion easily goes to completion. Thus, from Equation (6.18) we can write Al, = AH#(COz, ¢) ~ [AHGC, graphite) + AHZ(O>, g)] 393.5 ki/mol66 Standard Enthalpy of Formation and Reaction 255 Because both graphite and O; are stable allotropic forms of the elements, it follows that AH{(C, graphite) and AH7(O>, g) are zero. Therefore, 393.5 ki/mol Hq = AHi(CO>, 8) or AH{CO;, g) = —393.5 kl/mol Note that arbitrarily assigning zero AH? for each element in its most stale form at ‘the standard state does not affect our calculations in any way. Remember, in thermochem- isty we are interested only in enthalpy changes because they can be determined experi- mentally whereas the absolute enthalpy values cannot. The choice of a zero “reference level” for enthalpy makes calculations easier to handle. Again refering tothe temestrial altitude analogy, we find that Mt. Everest is 8708 fe higher than Mt. MeKinley. Tis df= ference in alitude is unaffected by the decision to set sea level at 0 ft or at 1000 ft. Other compounds that can be studied by the direct method are SF, PsO, and CS, The equations representing their syntheses are Sthombic) + 3F.(g) — Sea) Pa(white) + $02(8) —> P,Orx(8) CCgraphite) + 28(chombie) —> CS,(0) Note that S(chombic) and P(white) are the most stable allotropes of sulfur and phos- phorus, respectively, at | atm and 25°C, so their AH values are zero. The Indirect Method Many compounds cannot be directly synthesized from their elements. In some cases, the reaetion proceeds too slowly, of side reactions produce substances other than the desired compound. In these cases, AM? can be determined by an indirect approach, Which is based on Hess's law of heat summation, or simply Hess's law, named after the Swiss-Russian chemist Germain Hess." Hess's law can be stated as follows: When reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one sep or in a series of steps. In ther words, if we can break down the reaction of interest into a series of reactions for which AH, can be mensured, we can calculate AH, for the overall reaction. Hess's law is based on the fact that because HT is a sate function, A depends only on the inital and final state (that i, only on the nature of reactants and products). The enthalpy change would be the same Whether the overall reaction takes place in one step or many steps. ‘An analogy for Hess's law is as follows. Suppose you go from the first floor to the sixth floor of a building by elevato, The gain in your gravitational potential energy (wich ccomesponds to the enthalpy change for the overall process) is the same whether you g0 leet there or stop at each floor on your way up (breaking the trip into a series of steps). Let's say we aro interested in the standard enthalpy of formation of carbon mon- oxide (CO). We might represent the reaction as C(graphite) + 30x(@) —> CO(g) However, buming graphite also produces some carbon dioxide (CO;), so we cannot measure the enthalpy change for CO directly as shown. Instead, we must employ an indirect route, bused on Hess’s law. It is possible to carry out the following two separate reactions, which do go to completion: @ C(graphite) + Ox(g) —> CO;(g) AH = ~393.5 kI/mol ©) CO(g) + 10s(g) —+ CO3(g) AH = ~283.0 kimo} ‘Germain Hows Hess (1802-1880), Swiss-Russan chemist Hess was born in Switzerland but spent most of his ie in Russia, For formulating Hess's law, be is called the father of thermochemistry. White phosohors burns in iro fom 2.0.How a Bombardier Beetle Defends Itself erin isnot wn wl nia a ly competitive environment take many forms. For example, chumeleons have developed the ability to change color to match theie suroundings and the butterfly Limentis has evolved into a form that mimics the poisonous and unpleasant-tasting monarch buttery (Danaus). A less passive defense mechanism is em- ployed by bombardier beetles (Brachinus), which repel preds tors with a “chemical spray.” The bombardir beetle has a par of glands atthe tp ofits abdomen. Each gland consists of two compartments. The inner ‘compartment contains an aqueous solution of hydroquinone and hydrogen peroxide, and the outer compartment holds a mixture ‘of enzymes, (Enzymes are biological molecules that can speed upa reaction.) When threatened, the beetle squeezes some fluid from the inner compartment into the outer compartment, where, in the presence of the enzymes, an exothermic reaction takes place: ©) CePlOHDsCag) + HyOsea) —> C4H.0; (ag) + 2H,0( soe To estimate the heat of reaction, let us consider dhe following steps (0) CHACOH),(ag) — CH.O3(ag) + Hale) AH? = 177 kSimol (© H0x(aq) — 1,00) + 40,(8) AIP = ~94.6xximot (@)Ha(g) +$0x(g) —> HO) AHP = ~286 /mo1 ‘we find that the heat of reaction for (a) is ose fr (b) (c), and (a). © A bombard beetle discharging 0 crea spy ‘Therefore, we write aH: H+ AH? + AHS = (177 ~ 94.6 ~ 286) ki/mol 204 Ki/mol ‘The large amount of heat generated is sufficient to bring the mixture ois boiling point. By rotating the tip ofits abdomen, the beetle can quickly discharge the vapor in the form ofa fine ‘mist toward an unsuspecting predator. In addition tothe thermal elfect, the quinones also act a a repellent to other insects and animals, One bombarder beetle carries enough reagents to pro- duce 20 to 30 discharges in quick succession, each with an au- ible detonation, Firs, we reverse Equation (b) to get COx(g) —> CO(g) + 4O2(g) AH, = +283.0 kI/mol Because chemical equations can be added and subtracted just like algebraic equations, ‘we carry out the operation (a) + (¢) and obtain (a) ‘C(graphite) + O.(g) —> CO,(g) Aig, = —393.5 kJ/mol © COs(g) —> CO(g) + 40:8) Aff, = +283.0 Ki/mol © C(graphite) + $0.(g) — CO(g) AH = —110.5 kimol 2566.6 Standard Enthalpy of Formation and Reaction 257 ‘Thus, AH{(CO) = —110.5 ki/mol. Looking back, we see that the overall reaction is the formation of CO, [Equation (a)), which can be broken down into two parts [Equa- tions (4) and (0). Figure 6.10 shows the overall scheme of our procedure. ‘The genecal rule in applying Hess's law is to arrange a series of chemical equa- tions (corresponding to a series of steps) in such a way that, when added together, all species will cancel except for the reactants and products that appear in the overall reaction. This means that we want the elements on the left and the compound of interest on the right of the arrow. Further, we often need to multiply some or all of the equations representing the individual steps by the appropriate coefficients Seu Cateulate the standard enthalpy of formation of acetylene (C3) from is elements 2c rape) + Hale) —> Cole) ‘Te equations for esch step andthe comesponding ently changes are @ ‘C(graphite) + Ox(e) —> COx(e) Adiga = ~393.5 i/mol © Hg) + 30,2) —> H,0(), Alfig = ~285.8 kV/mol © 2CaHa(g) + 50x(2) —> 4CO3(¢) + 2H,0(1) AHfzg = ~2598.8 kl/mol Strafegy Ove goal here is to calculate the enthalpy change for the formation of ‘GyHf from its elements C and Hp. The reaction does not occur directly, however, 0 we must use an indirect route using the information given by Equations (a), @), and ©). Solution Looking at the synthesis of C:H;, we need 2 moles of graphite as reactant ‘So we multiply Equation (a) by 2 to get © 2Cigraphite) + 20,(g) —> 2COs(e) Affi = 2(—~393.5 kifmol) 787.0 kel (Next, we need 1 mole of H, as a reactant and this is provided by Equation (b). Last, we need I mole of CH a8 a product. Equation (c) has 2 moles of C3Hy a8 a reactant $0 ‘we need to reverse the equation and di y 2: © 200x(8) + HOW) —> GHL(@) + 103) AHine 1(2598.8 Ki/mol) 1299.4 kshmol ‘Adding Equations (4), (b), end (€ together, we get 2€( graphite) + 20,(@) —> 200,68) 787.0 e/mol Bais) + }Ox(¢) — #200) 2858 ki/mol 2COx(g) + Hz0() —> Cotlx(g) + 30,(g) Aig = 12994 kftmol 2C(graphite) + Hi(g) —> CsH(s) ‘Afi = 726.6 Kol ‘Therefor, AH? = AHfz, = 2266 Lmol. The AH? vale means that wien 1 male of Cll, is synthesized from 2 moles of Claraphit) and 1 mole of H, 226.6 IS of heat are absorbed by the reacting system from the suroupdings. Thus, this is an endothe proces. Practice Exercise Calculate the standard enthalpy of formation of carbon disulfide (CS; from its elements, given that Cégraphite) + Ox(s) —> COx(8) Adz, = ~393.5 kifmol S(chombie) + 03¢) —> $03G) AHS. = ~296.4ki/mol CS,(1) + 30s{¢) —> COAG) + 280;(4) ANZ, = -1073.6 0/01 ‘We can calculate the enthalpy of reactions from the values of AH}, as shown in Example 6.10. cox) Figure 6.10 me eninaoy change or te formation of mole ‘9fCO; fom graphite and O, con be broken oon ito twa Stops ccoraing fo Hess fam, o@@e ature (3000°C} ond Used 0 weld metos258 ‘Chapter 6 « Thermochemistry ‘The motten ron formedin @ termite reaction is ran down ito ‘amola bedween the ends of wo rotrocd ras. On cootng te ras are welded together ‘Sintarprostoms: 654, 857 Suen sed ‘The thermite reaction involves aluminum and iron(ID) oxide 2AL(s) + Fe,0s(s) —> ALOs(s) + 2Fe) ‘This reaction is highly exothermic and the iquid iron formed is used to weld metals. Calculate the heat released in kilojoules per gram of Al reacted with Fe,O3. The AH? for Fe(!) is 12.40 kl/mol Strategy The enthalpy of a reaction isthe diference between the som of the enthalpies fof the products and the sum of the enthalpies of the reactants. The enthalpy of each species (reactant or product) is given by its stoichiometric coefficient times the standard enthalpy of formation ofthe species. Solution Using the given AH value for Fe() and other AH values in Appendix 3 and Equation (6.18), we write Alf, = (AH(ALO:) + 2OH}(Fe)] ~ [2AHHAD + AHA(Fe;03)] (=1669.8 k¥/mol) + 212.40 kifmol)] ~ [2(0) + (—822.2 kY/mol)] 8228 ki/mol ‘This is the amount of heat released for two moles of Al reacted. We use the following ratio 822.86 2 mol Al to convert to Klig Al. The molar mass of Al is 26.98 g, so ~82281 Lol AL 2mol AL“ 2698 g Al -15251/e (Check 1s the negative sign consistent with the exothermic nature of the reaction? As a quick check, we see that 2 moles of Al weigh about 54 g and give off about 823 19 of ‘heat when reacted with Fe;O;, Therefore, the hest given off per gram of Al reacted is, approximately ~830 10/54 g or ~154 Wig. Practice Exercise Benzene (C,H) burns in ar to produce carbon dioxide and liquid ‘water. Calculate the heat released (in kilojoules) per gram of the compound reacted with ‘oxygen. The standard enthalpy of formation of benzene is 49.04 kI/mol. Iheat released per gram of Al Review of Concepts Explain why reactions involving reactant compounds with positive AZZ values are ‘generally more exothermic than those with negative AH? values. Heat of Solution and Dilution ‘Although we have focused so far on the thermal energy effects resulting from chem- al reactions, many physical processes, such as the melting of ice or the condensa- tion of a vapor, also involve the absorption or release of heat, Enthalpy changes occur as well when a solute dissolves in a solvent or when a solution is diluted. Let us look at these two related physical processes, involving heat of solution and heat of dilution,6.7 Heat of Solution and Dilution 259 Heat of Solution In the vast majority of cases, dissolving a solute in a solvent produces measurable heat change. At constant pressure, the heat change is equal to the enthalpy change. The heat of solution, or enthalpy of solution, AHyu, is the heat generated or absorbed when a certain amount of solute dissolves in a certain amount of solvent ‘The quantity AHjoq represents the difference between the enthalpy ofthe final solution and the enthalpies of is original components (that is, solute and solvent) before they are mixed. Thus, 19) Hy = Hlte ~ Heanonens Neither Hip NOF Hoopes C08 be measured, but their difference, AF. can be read- ily determined in a canstant-pressure calorimeter, Like other enthalpy changes, MHyn is positive for endothermic (heat-absorbing) processes and negative for exothermic (heat-generating) processes. Consider the heat of solution of process in which an ionic compound is the solute and water is the solvent. For example, what happens when solid NaCl dis- solves in water? In solid NaCI, the Na” and CI” ions are held together by strong positive-negative (electrostatic) forces, but when a small crystal of NaC! dissolves, in water, the three-dimensional network of ions breaks into its individual units (The structure of solid NaC! is shown in Figure 2.13.) The separated Na” and Cl- ions are stabilized in solution by their interaction with water molecules (see Fig- ure 4.2). These ions are said to be hydrated. In this case water plays a role similar to that of a good electrical insulator. Water molecules shield the ions (Na* and CI") from each other and effectively reduce the electrostatic attraction that held them together in the solid state. The heat of solution is defined by the fol- lowing process NaCl(s) > Na" (ag) + C1 (ag) MH =? Dissolving an ionic compound such as NaCl in water involves complex interactions among the solute and solvent species. However, for the sake of analysis we can imagine that the solution process takes place in two separate steps, illustrated in Figure 6.11. First, the Na* and CI ions in the solid crystal are separated from each other and converted to the gaseous state: energy + NaCl(s) —> Na*(g) + C1-(e) The energy required to completely separate one mole of a solid ionic compound into gaseous ions is called laitice energy (U). The lattice energy of NaCl is 788 ki/mol, In other words, we would need to supply 788 KI of energy to break 1 mole of solid NaCl into I mole of Na* ions and 1 mole of CI” ions. Next, the “gaseous” Na” and CI ions enter the water and become hydrated: Na*(g) + Cl"(g) 22> Na*(ag) + CI(ag) + energy The enthalpy change associated with the hydration process is called the heat of hydration, Aya, (beat of hydration is a negative quantity for cations and anions). Applying Hess's law, it is possible to consider AA, as the sum of two related quantities, latice energy (U) and heat of hydration (AAyyq), as shown in Figure 6.11 MFhiy = U + AHliyae (620) Inscoce oftleted ps occa by ‘onal eregurtern Late energy [So postive unt. wore et te260 ‘Chapter 6 Thermochemistry @e. @ e@ @&e 6 [Nat and C1 ions ia the gaseous state @ 4 — == — ae & er ee med SS woes ae “ef ae peta Pon Figure 6.11 The solution process for NaCl. The process can be considered to accur in two separate steps: (9 separation of ions from the cntal state fo the gaseous state and (2) hydration of the gaseous fos, The Neat of solution is equal fo the energy changes for these M0 Steps, Abn = U > AHyan ‘Therefore, NaCl(s) —> Nat(g) + C-(@) U= 788 ki/mot Na"(g) + C1"(g) 2 Na*(ag) + CI-(ag) _AFliyge = —784 kif/mnol NaCl(s) 2+ Na*(ag) + CI"(ag) Aq = 4 kI/mol ‘Thus, when 1 mole of NaCl dissolves in water, 4 KI of heat will be absorbed from the surroundings, We would observe this effect by noting that the beaker containing the solution becomes slightly colder. Table 6.5 lists the Ay of several ionic com- pounds. Depending on the nature of the cation and anion involved, APfas, for an ionic ‘compound may be ether negative (exothermic) or positive (endothermic). SE io ome ‘AH, __USe the data in Appendix 3 to calculate the heat of solution forthe following Compound —_{ks/moly Process: KNO3(s) —> K* (aq) + NO3 (aq) cl 31 CaCl, #28 NaCl 40 rl 172. Heat of Dilution NHLCI 152 When a previously prepared solution is diluted, that is, when more solvent is added NELNO; 266 10 lower the overall concentration of the solute, additional heat is usually given off cr absorbed. The heat of dilution is the heat change associated with the dilution‘A.Look Back at the Essential Knowledge 261 process, Ia certain solution process is endothermic and the solution is subsequently diluted, more heat will be absorbed by the same solution from the surroundings. The converse holds true for an exothermic solution process—more heat will be liberated if additional solvent is added to dilute the solution. Therefore, always be cautious when working on a dilution procedure in the laboratory. Because of its highly exo- thermic heat of dilution, concentrated sulfuric acid (H,SO,) poses a particularly haz~ ardous problem if its concentration must be reduced by mixing it with additional ‘water, Concentrated H;SO, is composed of 98 percent acid and 2 percent water by ‘mass. Diluting it with water releases considerable amount of heat to the surroundings. ‘This process is so exothermic that you must never attempt to dilute the concentrated acid by adding water to it. The heat generated could cause the acid solution to boil and splatter. The recommended procedure is to add the concentrated acid slowly to the water (while constantly string). Pome eee AU =q+w (61) PAV 63) U+PV 66) U + PAV (68) = ms 6.10) msAt (6.12) 4= Chr (6.13) AH, = Sn MHF (products) — SmAH; (reactants) (6.18) Atlan =U Aig (620) Mathematical statement of the first law of thermodynamics. Calculating work done in gas expansion or gas compress Definition of enthalpy. Calculating enthalpy (or energy) change for a ‘constant: pressure process. Definition of heat capacity. (Calculating heat change in terms of specific heat. Calculating heat change in terms of heat capacity Calculating standard enthalpy of reaction, Latice energy and hydration conteibutions to heat of solution. A Look Back at the Essential Knowledge Energy’ canbe transferred in a numberof ways including heat ‘or work. The total energy of the universe is constant according to the law of conservation of energy. The type, arrangement, and electrostatic interaction between particles determines the potential energy of atoms and molecules. This is stored energy ‘whiei can be converted, typically ito thermal, electical, and ‘mechanical energy. Heat is a measure of the transfer of energy from one body to another, associated witha change in temperature. ‘Any process that transfers heat o the surroundings i called lan exothermic process while a process that absorbs heat from the surroundings is known as an endothermic process. We define a system as that portion ofthe universe we wish to study. Everything else isthe suroundings. Adding heat 1 a system increases its energy content. A chemical reaction may provide thermal energy to the surroundings, an exothermic reaction, or the reaction may require thermal energy be transferred from the surroundings, an endothermic reaction. The internal energy ofa system is comprised ofthe Kinetic energy of motion of atoms, electrons, and molecules andthe potential energy of atraction between electrons and nuclei and repulsions between species. Internal enerpy of siven state cannot be directly measured. The first law of thermodynamics equates intemal energy tothe flow of work and heat to or from the system, Internal energy is state function and therefore independent ofthe path taken from its inital state to the final state while heat and work are path dependent. Enthalpy, A, i related to internal energy and is equal to AU + PAV for a constant pressure process, The change in enthalpy measures the heat given off or absorbed by ‘constant pressure process such asa reaction in a beaker Calorimetry is sed to experimentally measure heat flow of a process at constant pressure. Through calorimetry we can determine properties such a specific heat, non-combustion heats of reaction, heats of solution and of dilution and changes in physical state, Heats of formation are a measure ofthe heat released or absorbed by the formation of 1 mole ofa chemicel species from its constituent atoms in their standard state. The standard enthalpy of reaction can be determined using the ‘standard state enthalpy of formation for each reactant and product, incorrect molar proportions. The heat of solution is the sum of enthalpies required to seperate molecules or ions from the solid state and the enthalpies of hydration of each of the separated species. Hea of dilution isthe heat released or absorbed when a solution, such as an acid, is diluted. FALFOCUS REVIEW. GUIDE Complete the actutesn Chapter 6 of your AP Focus Review Guide to review content essential for your AP exam.262 ‘Chapter 6 « Thermochemistry LCA lees Calorimetry, p. 246 Fist law of ‘Chemical energy, p. 231 thermodynamics, p. 234 ‘Closed system, p. 232 Heat, p. 232 Endothermic process, . 233, ‘Heat capacity (C), p.246 Energy, p. 231 Heat of dilution, p. 260 Emthatpy (Hp. 241 Heat of hydration Enthalpy of reaction (QHlya) p- 259 (Adon. 242 Heat of solution Enthalpy of solution (Alas) P.259 (Hla) P: 259 less law, p. 255 Exothermie process, p.233 Isolated system, p. 232 Questions & Problems Lattice eneray (U),p. 259 Law of conservation of, energy, p. 231 Standard state, p.253 State function, p. 234 State ofa system, p. 234 (Open system, p. 232 ‘Surroundings, p. 232 Potential energy, p. 231 ‘System, p, 232 Radiant energy, p. 231 ‘Thermal energy, p. 231 Specific heat (3), p. 246 ‘Thermochemical Standard enthalpy of| equation, p. 243 formation (Aff), p.253__Thermochemisty,p. 232 Standard enthalpy of reaction Thermodynamics, p. 234 (Alfig)p. 253 ‘Work, p. 231 (© Problems avalable in Connect Plas ‘ed numbered problems solved in Student Solutions Manual 63 64 6s 66 Dein these tems: system, surroundings, open sys- tem, closed system, isolated system, thermal energy, chemical energy, potential energy. kinetic energy, law of conservation of energy. ‘What is heat? How does heat differ from thermal energy? Under what condition is heat ransferred from one system to another? ‘What are the units for energy commonly employed inchemisty? ‘A uckinitally waveling 2160 km perhouris brought toa.complet stop ata traffic light. Does this change ‘violate the law of conservation of energy’ Explain. ‘These are various forms of energy: chemical, heat, light, mechanical, and electrical. Suggest ways of {nterconverting these forms of energy. Describe the interconversons of forms of energy 0c curing in these processes: (a) You throw a softball up into the ar and catch it (b) You switch on a ashlight (©) You ride the ski lift to the top ofthe bill and then ski down. (4) You trike a match and let it bur dow, Energy Changes in Chemical Reactions Review Questions © 6.7 Define these terms: thermochemistry, exothermic process, endothermic process. 68 Stoichiometry is based on the law of conservation of ‘mass, On what law is thermochemistry based? 69 Describe two exothermic processes and two endo- thermic processes. 6.10 Decomposition reactions are usually endothermic, Whereas combination reactions are usually exother- mic, Give a qualitaive explanation for these tends. First Law of Thermodynamics Review Questions 61 e614 (On what law is the first law of thermodynamics ‘based? Explain the sign conventions in the equation AU=q+w. Explain what is meant by a state function. Give two examples of quantities thet are state functions and two that are not, ‘The internal energy of an ideal gas depends only on its temperature. Do a fist-law analysis of this process. A sample of an ideal gas is allowed to ex- ppand at constant temperature against atmospheric pressure. (a) Does the gas do work on its surround- ings? (b) Is there heat exchange between the sys- tem and the surroundings? Ifs0, in which direction? (©) What is AU forthe gas for this process? Consider these changes. (@ Hg) — Hee) (b) 30,¢) —> 20,66) (©) CuSO, - $H,0(s) —> CuS0,(s) + SH;O(¢) (@) Ha(g) + Fa(g) —> 2HF Ce) At constant pressure, in which of the reactions is ‘work done by the system on the surroundings? By the surroundings on the system? Ta which of them is no work done? Problems © 6.15 $6.16 A sample of nitrogen gas expands in volume from 1.6L to 54 Lat consiant temperature, Calculate the ‘work done in joules if the gas expands (a) against a ‘vacuum, (b) against a constant pressure of 0.80 atm, and (6) against a constant pressure of 3.7 atm, ‘A gas expands in volume from 26.7 mL to 89:3 mL. at constant temperature. Calculate the work done (in joules) if the gas expands (a) egainst a vacuum, (b) against a constant pressure of 1.5 atm, and (© against a constant pressure of 2.8 atm.$617 #618 6.19 6.20 A gas expands and does P-V work on the surround- {ngs equal to 325 I. Atthe same time, it absorbs 127 1 cof heat from the surroundings. Calculate the change in energy of the gas. ‘The work done to compress a gas is 74J. Asa result, 26 J of heat is given off to the surroundings. Caleu- late the change in energy ofthe gas. CCaleulate the work done when 50.0 g of tin dis- solves in excess acid at 1,00 atm and 25°C: Sn(s) + 2H*(ag) —> Sn?*(ag) + Hag) Assume ideal gas behavior CCaleulate the work done in joules when 1.0 mole of water vaporizes at 1.0 atm and 100°C. Assume that the volume of liquid water is negligible compared ‘with that of steam at 100°C, and ideal gas behavior. Enthalpy of Chemical Reactions Review Questions 621 622 623 624 Define these terms: enthalpy, enthalpy of reaction. ‘Under what condition isthe heat ofa reaction equal to the enthalpy change of the same reaction? In writing thermochemical equations, why is it im- portant to indicate the physical state (that is, gas e0us, liquid, solid, or aqueous) of ezch substance? Explain the meaning ofthis thermochemical equation: ANIL) + $0x(g) —> 4NO(e) + 6H0(8) AH = ~904 Klima ‘Consider this reaction: 2CH,OH(D) + 303(g) —> 41,00) + 2C0x(@) AH = ~1452.8ki/mo! What isthe value of A/T if (2) the equation is multi- plied throughout by 2, (6) the dircction of the rac- tion is reversed so that the products become the reactants and vice versa, (c) water vapor instead of liquid water is formed as the product? Problems #625 96.26 86.27 ‘The first step in the industrial recovery of zine from the zine sulfide ore is roasting, that is, the conver: sion of ZnS to Zn0 by heating: 2L08(s) + 303(g) —> 220016) + 20:18) AH = 8791/01 Calculate the heat evolved (in IJ) per gram of ZnS roasted Determine the amount of heat (in k) given off when 1.26 x 10° g of NO, are produced according to the equation 2NO(e) » 2NOx(8) AH = ~1146 kd/mol x8) Consider the reaction 2H,0(g) —> 2Ha(g) ++ O(8) AH = 483.6 43/mol $6.28 Questions & Problems 263 If 2.0 moles of H,O(g) are converted to Ha(g) and (04(g) against a pressure of 1.0 atm at 125°C, what is AU for this reaction? Consider the reaction H.(g) + Ch(g) — 2HCKg) AH = ~184.6 3/mol 1f 3 moles of H, react with 3 moles of Cla to form HCI, calculate the work done (in joules) against @ pressure of 1.0 tm at 25°C. What is AU for this re- action? Assume the reaction goes to completion, Calorimetry Review Questions 629 630 What is the difference between specific heat and hheat capacity? What are the units for these two quantities? Which is the intensive property and Which i the extensive property? Define calorimetry and describe wo commonly used calorimeters. In calorimetric measurement, why is it important that we know the heat capacity ofthe calorimeter? How is this value determined? Problems #631 #632 #633 9634 #635 Consider the following data Metal A Mass (@) 0 30 Specifichest W/g-°C) 0.900 0.385 “Temperature CC) 0 6 ‘When these two metals are placed in contact, which of the following will tke place? (a) Heat will flow from Al to Cu because Al has ‘larger specific heat. (b) Heat will flow from Cu to Al because Cu has larger mass. (©) Heat will flow from Cu to Al because Cu has a larger heat capacity (@) Heat will flow from Cu to Al because Cu is at a higher temperature. (©) Noheat will flow in either direction. A piece of silver of mass 362 g has @ heat capacity ‘of 85.7 IPC, What is the specific heat of silver? A 622-kg piece of copper metal is heated from 20,5°C to 324.3°C. Calculate the heat absorbed (in J) by the metal, Calculate the amount of heat liberated (in kd) from 366 g of mercury when it cools from 77.0°C 10 12.0°C. A sheet of gold weighing 10.0 g and at a temperature of 18.0°C is placed Mat on a shect of iron weighing 20.0 g andat a temperature of 55.6°C. Whats the final ‘temperature of the combined metals? Assume that no ‘hea is lost to the suroundings. (Hint: The heat gained by the gold must be equal 1 the heat lost by the iron. ‘The specific heats ofthe metals are given in Table 6.2.)264 Chapter 6 « Thermochemistry 6.36 Toasample of water at23.4°C in aconstant-pressure calorimeter of negligible heat capacity is added a 12.L-g piece of aluminum whose temperature is 817°C. Ifthe final temperature of water is 24.9°C, calculate the mass of the water in the calorimeter. (Hint: See Table 6.2.) 637 A0.1375-g sample of solid magnesium is bumed in ‘ constant-volume bomb calorimeter that has a heat capacity of 3024 JPC. The temperature increases by 1.126°C. Calculate the heat given off by the buming Mg, in kl/g and in kl/mol © 6.38 A quantity of 85.0 ml of 0.900 M HClis mixed with 850 mL of 0.900 M KOH in a constant-pressure calorimeter that has a heat capacity of 325 JPC. If the initial temperatures of both solutions are the same at 18.24°C, what is the final temperature of the mixed solution? The heat of neutralization is $6.2 ki/mol. Assume the density and specific heat of the solutions are the same as those for water. Standard Enthalpy of Formation and Reaction Review Questions 6.39 What is meant by the standard-state condition? 640 How are the standard enthalpies of an element and of a compound determined? 641 Whatis meant by the standard enthalpy of «reaction? 642 Write the equation for calculating the enthalpy of a reaction. Define all the terms 643 State Hess's law. Explain, with one example, the usefulness of Hess's law in thermochemistry. 6.44 Describe how chemists use Hess's law to determine the AH? of a compound by measuring its heat (en- thalpy) of combustion. Problems 645 Which ofthe following standard enthalpy of forma tion values is not zero at 25°C? Nas), Ne(g),CH.Ca), 5460, He, HU) AG The AH vals ofthe two allotropes of oxygen, O; and Oy, ace O and 142.2 ki/mol, respectively, at 25°C. Which is the more stable form at this temperature? 647 Which is the more negative quantity at 25°C: ANE for Hi0()) or AH? for H,0(8)? © 6.8 Predict the value of AA? (greater than, less than, oF equal t2er0) for these elements at 25°C: (a) Bete): Br(). ©) La) LO). 6.49 In genera, compounds with negative AH values are tore stabie than those with positive AI; values. ,0,() has a negative AM (see Table 6.4). Why, then, does H,0,() have a tendency to decompose 0 H,0() and 0.@)? 6.50 Suggest ways (with appropriate equations) that ‘would enable you to measure the AH? values of ‘Ag0(s) and CaCl,() from their elements. No eal- calations are necessary #651 9652 9653 654 $655 $6.56 657 #658 Calculate the heat of decomposition fo this process at constant pressure and 25°C: CaCOs(8) —> CaOLs) + COs) (Look up the standard enthalpy of formation of the reactant and products in Table 6.4.) ‘The standard enthalpies of formation of ions in aqueous solutions are obtained by arbitrarily as- Signing a value of zero to H” ions; tht is, APTI (ag)) = (a) For the following eaction Hcg) 2 HY (ag) + Ar cr (ag) 749 ki/mol calculate AH? forthe CI” ions (©) Given that AHf?for OH" ions is ~229.6 KYmol, calulate the enibelpy f neutralization when T mole ofa strong monoprotic acid (such as HC} is ttated by I mole of a strong base (such as KOH) at 25°C Calculate the heals of combustion forthe following reactions from the standard enthalpies of formation listed in Appendix 3: (@) 2H) + Og) — 24:00 (©) 2C3H,(8) + 50;() —+ 4C0,() + 21,00 Calculate the heats of combustion forthe following reactions from the standard enthalpies of formation listed in Appendix 3: (@) CaHi(g) + 30,(g) —> 2004(¢) + 21,000) (6) 2H,S(@) + 30;(@) — 2H,0() + 280,(8) Methanol, ethanol, and n-propanol are three com- ‘mon aleohols. When 1.00 of each ofthese alcohols js burned in aie, heat is liberated a8 shown by the following data: (a) methanol (CH,OH), ~22.6 kl: (©) ethanol (C:H,OH), ~29.7 W; (€) mpropanol (CHH,OH), ~33.4 KI. Caleulate the heats of com- bbustion of these alcobols in ki/mol ‘The standard enthalpy change forthe following re- setion is 436.4 Kimo: Haig) —> Hig) + Hig) Calculate the standard enthalpy of formation of atomic hydrogen (HD. From the standard enthalpies of formation, calculate AH for the reaction Cali) + 9036) —> 6CO,(e) + 61,00) For CHi(, AH? = -151.9 ki/mol Pentaborane-9, BsHp, is a colorless, highly reactive liquid that will burst into flame when exposed to oxygen. The reaction is, 2BGHy(D) + 120318) —> 5B,0\65) + 9H,00 Calculate the klojoules of heat released per gram of the compound reacted with oxygen. The standard ceathalpy of formation of BsH, is 73.2 kif,#659 + 6.60 © 661 = 6.62 #663 Determine the amount of heat (ink) given off when 1.26 X 10! g of ammonia are produced according to the equation Nala) + 3H3(@) —> 2NHI(@) Ain = ~92.6 kifmot ‘Assume thatthe reaction takes place under standard state conditions at 25°C. At850°C, CaCO; undergoes substantial decomposi- tion to yield CaO and CO,, Assuming thatthe AH? values of the reactant and products are the same at 850°C as they are at 25°C, calculate the enthalpy change (in KJ) if 66.8 g of CO; are produced in one reaction From these data, ‘S(shombic) + Ox(g) —> $0,(8) AHizy = ~296.06 kd/mol ‘S(monoctinic) + Ox(¢) —> SOx(2) Ming = ~296,36 k3/mol calculate the enthalpy change forthe transformation ‘S(shombic) —> $(monoclinie) (Monoclinic and rhombic are different allotropic forms of elemental sulfur) From the following data, C(graphite) + Ox(g) —+ COxs) AHfzn = ~393.5 kS/mol Ho(g) + $0a(g) —> HOW) Alyy = =285.8 mol 2CHa(g) + TOx(g) —> 4C03(e) + 64,01) 3119.6 kml calculate the enthalpy change for the reaction 2C(araphite) + 3H4(g) —> C.tg(a) From the following heats of combustion, CHOH() + $0,() —> CO,(@) + 28,00) Ai, = ~7264 kS/mol (graphite) + Ox(¢) —> COx(e) =398.5 imal Hats) + 103g) —> 100) AF = ~285.8 K/mol caleulate the enthalpy of formation of methanol (CH,OH) from its elements: (graphite) + 2Ha(@) + 40:2) — CHLOHU) Calculate the standard enthalpy change fr the reaction 2AM) + Fe0x6s) —> 2Fe(s) + AOs(s) sven that 2AL(s) + 30x(g) —> ALOx(s) Afzy = ~1669.8 kSmol 2Pe(s) + 03(¢) —> PesOals) Aig = ~822.2 k/mol Questions & Problems 265 Heat of Solution and Dilution Review Questions 6.65 6.66 667 6.68 669 670 Define the following terms: enthalpy of solution, heat of hydration, lattice energy, heat of dilution. ‘Why isthe lattice energy of a solid always a positive quantity? Why isthe hydration of ions always a neg- ative quantity? Consider two ionic compounds A and B.A has a larger lattice energy than B. Which of the two com: pounds is more stable? Mg*" is a smaller cation than Na‘ and also carries more positive charge. Which of the two species has larger hydration energy (in kifmol)? Explain. ‘Consider the dissolution of an jonic compound such as potassium fluoride in water. Break the process into the following steps: separation of the cations ‘and anions in the vapor phase and the hydration of the ions in the aqueous medium. Discuss the energy changes associated with each step. How does the heat of solution of KF depend on the relative magni- tudes of these two quantities? On what law is the relationship based? ‘Why is it dangerous to add water to a concentrated acid such as sulfuric acid in a dilution process? Additional Problems on 672 673 678 wos 6.16 ‘Which ofthe following does not have AH? = 0 at 25°C? Helg) Pets) Cle) Sx) Ox) BAD Calculate the expansion work done when 3.70 moles of ethanol are converted to vapor tis boiling pint (78.3°C) and 1.0 atm, ‘The convention of arbitrarily assigning a zero en- thalpy value for the most sabe form ofeach element in the standard state at 25°C is convenient way of dealing with enthalpies of reactions. Explain why this convention cannot be applied to nuclear reactions. Given the thermochemical equations Br(D) + FG) —> 2818) a= Bry(D) + 3Fs(e) —> 2Be(g) AHP = ~768 i/o) calculate the AH for the reaction BrP) + Fu(g) — BF) ‘The standard enthalpy change AH® forthe thermal decomposition of silver nitrate according tothe fol- Jowing equation is +7867 I: AgNO4(s) —> AgNOX() + 40368) ‘The standard enthalpy of formation of AgNO) is = 123.02 ki/mol. Caleulae the standard enthalpy of formation of AgNOx). ydrazine, NaH, decomposes according tothe fol lowing reaction: BNGHA(D) —> 4NH(g) + Ne) 188 ki/mol266 om 678 6.79 = 680 681 682 © 683 = 684 ‘Chapter 6 + Thermochemistry (a) Given thatthe standard enthalpy of formation of hydrazine is 50.42 kI/mol, calculate AH for its de- composition. (b) Both hydrazine and ammonia bum in oxygen to produce H,0(P) and N,(g). Write bal ‘anced equations for each of these processes and cal- culate AH” for each of them. On a mass basis (per kg), would hydrazine or ammonia be the beter fuel? ‘A quantity of 2.00 10? mL of 0.862 M HCI is ‘mixed with an equal volume of 0.431 M Ba(OR) in 44 constant-pressure calorimeter of negligible heat capacity. The initial temperature of the HCland Bu(OH), solutions is the same at 20.48°C, For the process H(ag) + OH" (ag) —> 1,00 the heat of neutralization is ~$6.2 kI/mol. What is the final temperature of the mixed solution? A.3.53-g sample of ammonium nitrate (NH.NO3) ‘was added to 80.0 mL. of water in a constan ‘pressure calorimeter of negligible heat capacity. AS 2 result, the temperature of the water decreased from 21.6°C to 18.1°C. Calculate the heat of solution (GH) of mmonium nitrate ‘Consider the reaction Nalg) + 3Ha(g) —> 2NHs(@) Alig = = 92.6 S/mol 1f2.0 moles of Nz react with 6.0 moles of Hs to form. [NI calculate the work done (in joules) against a pressure of 1.0 atm at 25°C. What is AU for this re= action? Assume the reaction goes to completion Calculate the heat leased when 2.00 of Cle) 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, Photosynthesis produces glucose, CjHi:Os, and ‘oxygen from carbon dioxide and water: 6CO; + 6HO —> CyH,05 + 60; (2) How would you determine experimentally the AW, value for this reaction? (b) Solar radiation produces about 7.0 X 10" kg glucose a year on Earth, What is the corresponding BA change? A2.10-mole sample of erystalline acetic acid, ini tially at 17.0°C, is allowed to melt at 17.0°C and is then heated to 118.1°C (ts normal boiling poi) at 1.00 atm, The sample is allowed to vaporize at 118.1°C and is then rapidly quenched to 17.0°C, s0 that it rerystallizes. Calculate AH? fr the total pro- cess as dseribed Calculate the work done in joules by the easton 2Na(s) + 2H,O() —> 2NeOHCag) + Has) when 0.34 g of Na resets with wate to form hydro- gen gas at °C and 1.0 atm ‘You are given the following data: Hx(g) > 2H(g) ANP = 436-4 1o/mol Brig) —> 2Brig) AA = 192.5 k/mol Hy(a) + Bro(g) —> 2HBr(g) ane 724 Weal 6.85 6.86 #687 © 6.88 © 689 6.90 = 691 Calculate AA? forthe reaction H(g) + Br(g) —> HBr(g) {A guscous mixture consists of 284 mole percent of hydrogen and 71.6 mole percent of methane. A 15.6L gas sample, measured at 19.4°C and 2.23 atm, is twumed in ar Caleuate the heat release, When 2.740 g of Ba reacts with Op at 298 K and 1 atin to form BuO, 14 kJ of heat are released. Whats AH? for BaO? Methanol (CH;OH) is an organic solvent and is also used as fue in some automobile engines. From the following data, calculate the standard enthalpy of formation of methanol 2CHLOH() + 30,(2) —> 2COx(g) + 44,00) AH, = 1452.8 ki/mol A.44,0-g sample of an unknown metal at 99.0°C was placed in a constant-pressure calorimeter containing 80.0 g of water at 24.0°C. The final temperature of the system was found to be 284°C. Calculate the specific heat of the metal. (The heat capacity of the calorimeter is 12.4 JP°C.) Using the data in Appendix 3, calculate the enthalpy change for the gaseous reaction shown here. (Hint: First determin the lim @co @x ex. Producer gas (carbon monoxide) is prepared by passing air over red-hot coke: C(s) + 4Ox(g) —> CO(g) ex. Water gas (mixture of carbon monoxide and hydro- _gen) is prepared by passing steam over red-hot coke: C{s) + H:0() —+ COL) = Hg) For many years, both producer gas and water ges were used as fuels in industry and for domestic ‘cooking. The large-scale preparation of these gases was cartied out alternately, that is, first producer 25, then water gas, and s0 on. Using thermochem- ical reasoning, explain why this procedure was choses ‘Compare the heat produced by the complete com- bustion of I mole of methane (CH,) with a mole of ‘water gas (0.50 mole H, and 0.50 mole CO) under the same conditions. On the basis of your answ ‘would you prefer methane over water gas as a fuel? Can you suggest two other reasons why methane is preferable to water gas asa fuel?9692 © 693 + 6.94 695 46.96 697 © 6.98 699 6.100 ‘The so-called hydrogen economy is based on hydro- gen produced from water using solar energy. The {gas may be burned as a fuel: 2Hlg(g) + Os(8) —> 24%,0(F) A primary advantage of hydrogen as a fuel is that it js nonpolluting. A major disadvantage is that iis a 40s and therefore is harder to store than liquids or Solids. Calculate the volume of hydrogen gas at 25°C and 1.00 atm required to produce an amount of energy equivalent to that produced by the eombus- tion of gallon of octane (CiEhs). The density of cctane is 2.6 kg/gal, and its standard enthalpy of formation is ~249.9 k/mal Ethanol (C:H0H) and gasoline (assumed to be all octane, C,H}, are both used as automobile ful. IF ‘gasoline is selling for $4.5O/gal, what would the price of ethanol have to be in onder to provide the same amount of heat per dollar? The density and ‘AH? of octane are 0.7025 g/ml. and ~249.9 ki/mol and of ethanol are 0.7894 g/mL and ~277,0 k/mol, respectively. | gal = 3.785 L. The combustion of what volume of ethane (Ci, measured at 230°C and 752 mmHg, would be required ioheat 855 go water from25.0°C 10 980°C? If energy is conserved, how can there be an energy ‘The heat of vaporization of a liquid (AA) is the energy required to vaporize 1.0 8 ofthe liquid at its boiling point. In one experiment, 600 ¢ of Liquid siteogen (boiling point ~ 196°C) are poured into a Styrofoam cup containing 2.00 X 10% g of water at $5.3°C. Caleulate the molar heat of vaporization of liquid nitrogen if the final temperature of the water is 410°C. Explain the cooling effect experienced when ethanol isrubbed on your skin, given that CHOH() —> GsHLOH(g) AH? = 42.2 Kd/mol For which of the following reactions does APfgg = AH? (@) Hyg) + S(chombic) —> H,S(g) (©) C(diamond) + Ox(¢) —> COxLe) (©) Ha(g) + CuO(s) —+ 1,00) + Cals) (@) O(8) + Ox(2) —> Ox) Calculate the work done (in joules) when 1.0 mole of water is frozen at 0°C and 1.0 atm. The volumes of one mole of water and ice at °C are 0.0180 L and 0.0196 L, respectively. A quantity of 0,020 mole of a ga initially at 0.050 L and 20°C undergoes & constant-temperature expan= sion until its volume is 0.50 L. Calculate the work done (in joules) by the gas if it expands (a) against vacuum and (b) against a constant pressure of (0.20 atm. (c) Ifthe gas in (b) is allowed to expand unchecked until its pressure is equal to the external pressure, what would its final volume be before it stopped expanding, and what would be the work done? ©6101 6.102 6.103 96.108 © 6.105 + 6.106 96.107 * 6.108 Questions & Problems 267 Calculate the standard enthalpy of formation for dia- ‘mond, given that C(gruphite) + O;(2) —+ CO,(8) AH* = —3935 1/mol (diamond) + O3(s) —> COx(g) AHP = ~3954 ki/mol (@) For most efficient use, refigerator freezer com- partments should be fully packed with food. What is the thermochemical basis for this recommendation? (b) Starting at the same temperature, tea and coffee remain hot longer in a thermal flask than chicken noodle soup. Explain Calculate the standard enthalpy change for the fer- ‘mentation process. (See Problem 3.72.) Portable hot packs are available for skiers and peo- ple engaged in other outdoor activities in a cold cli- ‘mate. The air-permeable paper packet contains a mixture of powdered iron, sodium chloride, and other components, all moistened by a little water. ‘The exothermic reaction that produces the heat is a very common one—the rusting of iron: > 2Fe,0s(5) When the outside plastic envelope is removed, O molecules penetrate the paper, causing the reaction to begin. A typical packet contains 250 g of iron to warm your hands or feet for up to 4 hours. How ‘much heat (in kJ) is produced by this reaction? (Hint: See Appendix 3 for AH values.) ‘A person ate 0.50 pound of cheese (an energy intake cof 4000 Ki). Suppose that none of the energy was stored in his body. What mass (in grams) of water ‘would he need to perspire in order to maintain his original temperature? (It takes 44.0 Id to vaporize mole of water) ‘The total volume of the Pacific Ocean is estimated to be 7.2 X 10° km’. A medium-sized atomic bomb produces 1.0 X 10° J of energy upon explosion. Caleulate the umber of atomic bombs needed to release enough energy to raise the temperature of the water in the Pacific Ocean by 1°C. A 19.2-g quantity of dry ice (solid carbon diox- {de) is allowed to sublime (evaporate) in an appa- ratus like the one shown in Figure 6.5. Caleulate the expansion work done against a constant exter- nal pressure of 0.995 atm and at a constant tem perature of 22°C. Assume that the initial volume of dry ice is negligible and that COs behaves Tike ‘an ideal gas. ‘The enthalpy of combustion of benzoie acid (CJH,COOH) is commonly used as the standard for calibrating constant-volume bomb calorimeters; its value has been accurately determined to be =3226.7 ki/mol. When 1.9862 g of benzoic acid are bbumed in a calorimeter, the temperature rises from 21,84°C to 25.67°C. What is the heat capacity ofthe bomb? (Assume that the quantity of water surround= ing the bomb is exactly 2000 g,) 4Fe(s) + 30,(¢)268 © 6.109 #6110 61 #6112 6113 6.18 6415 Chapter 6 « Thermochemistry ‘The combustion of a 25.0-g gaseous mixture of Hy and CH, releases 2354 10 of heat. Calculate the amounts ofthe gases in grams. Calcium oxide (CaO) is used to remove sulfur diox- ‘de generated by coal-burning power stations: 2Ca0(s) + 280x(8) + Oxtg) —> 2CaS0Ks) Calculate the enthalpy change for this process if 6.6 X 10° g of SO, are removed by this process every day. Glauber’s salt, sodium sulfate decahydrate (Na;SO,* 10H,0), undergoes a phase transition (that is, ‘melting or freezing) at a convenient temperature of about 32°C: [NapS0, + 10H,0(s) —> Naj$O, + 10H,0(0) ‘AH? = 74.4 kl/mol ‘As a result this compound is used to regulate the temperature in homes. It is placed in plastic bags in the ceiling of a room. During the day, the endother- ‘mic melting process absorbs heat from the surround- ings, cooling the room. At nigh, it gives off heat as it freezes. Calculate the mass of Glauber’s salt in kilograms needed to lower the temperature of ait in a room by 8.2°C at 1.0 atm. The dimensions of the room are 2,80 m X 10.6 m X 17.2 m, the specific heat of air is 1.2 ig + °C, and the molar mass of air ‘may be taken as 29.0 g/mol {A balloon 16 m in diameter is inflated with helium at 18°C. (a) Calculate the mass of He in the balloon, assuming. ideal behavior. (b) Calculate the work ‘done (in joules) during the inflation process if the atmospheric pressure is 98.7 kPa Acetylene (CoH;) can be hydrogenated (reacting ‘with hydrogen) first to ethylene (C3EL,) and then to ethane (C,H). Starting with one mole of CH, label the diagram shown here analogous to Figure 6.10. ‘Use the data in Appendix 3, Calculate the AH” forthe reaction Fe (ag) + 30H7(ag) —> Fe(OWD)s68) ‘An excess of zinc metal is added to $0.0 mL. of a 0.100 Mf AgNO, solution in a constant-pressure cal- corimeter like the one pictured in Figure 6.9. AS a result ofthe reaction Za(s) + 2Ag" (aq) —> Za?” (aq) + 2Ag(3) 6.116 6al7 6.18 6.119 6.120 ela the temperate rises from 1925°C to 22.17. If the heat capacity of the calorimeter is 98.6 IFC, cal- culate the enthalpy change for the above reaction on 4 molar basis. Assume thatthe density and specific heat ofthe solution are the same as those for water, and ignore the specific heats of the metals (9 A person drinks four glasses of cold water {G.0°O) every day. The volume of each glass is 25 x 10% mL How much heat (in) does the body have to supply to rise the temperature ofthe water to 37°C, the body temperature? (6) How mach heat sould your body lose if you were to ingest 8.0 10? g of snow at O°C to quench thes? (The amount of heat necessary to melt snow is 6.01 kJ/mol.) A diver’ manual states thatthe stopping distance «quadruples asthe speed doubles hati takes 30 {to stop a cae moving t 25 mph then t woud take 120 feto sop car roving at 50 mph Justi this sttementby sing mechanics andthe fst aw ofthe ‘modynamics. (Assume that when a aris stopped, ts Kinetic energy (Jn) is ally converted o het [At 28°, the standard enthalpy of formation of ‘HF (aq) is given by ~320.1 kJ/mol; of OH” (ag), itis ~229.6 emo of F-(ag, itis ~329.1 Kimo and of H,0(), itis ~285.8 Kimol (@) Caleaat the standard enthalpy of neutralization of HF(aq): HF (aq) + OH" (ag) —> F(aa) + H,00) (©) Using the value of ~56.2 KI as the standard enthalpy change forthe reaction H (ag) + OH (ag) — HOW) calculate the standard enthalpy change forthe reaction HF(ag) —> H"(ag) + Fag) ‘Why are cold, damp air and hot, humid sir more un- ‘comfortable than dry air at che same temperatures? (The specific heats of water vapor and air are approx imately 1.9 Yg~°C and 1.0J/g °C, respectively.) ‘From the enthalpy of formation for CO, and the fol- lowing information, calculate the standard enthalpy ‘of formation for earbon monoxide (CO). CO(g) + 102g) — COxe) ANP = =283.0kt/mot Why can’t we obtain it directly by measuring the enthalpy of the following reaction? (graphite) + $0,(2) —> COVE) ‘A 46k pesson drinks 500 of milk, which has a “caloric” value of approximately 3.0 Wig. I only 17 percent ofthe energy in milks converted to me- chanical work, how high (in meters) can the person limb based on this energy intake? [fin The work done in ascending is given by mh, where m isthe mass (i kilograms), g the gravitational scceera tion (9.8 ms"), and the height in meters)+6422 #6123 6.124 6.125 © 6.126 6127 6.128 ‘The height of Niagara Falls on the American side is 51 m. (a) Calculate the potential energy of 1.0 g fof water at the top of the falls relative to the ground level. (b) What is the speed of the falling water if all of the potential energy is converted to kinetic energy? (c) What would be the increase in temperature of the water if all the kinetic energy ‘were converted to heat? (See Problem 6.121 for suggestions.) In the nineteenth century two scientists named Dulong and Pett noticed that fora solid element, the product of its molar mass and its specific heat is approximately 25 J°C. This observation, now called Dulong and Pedt’s law, was used to estimate the spe- cific heat of metals, Verify the law for the metals listed in Table 6:2. The law does not apply to one of the metals. Which one is it? Why? Determine the standard enthalpy of formation of ethanol (CH,OH) from its standard enthalpy of ‘combustion (=1367.4 ki/mo Acetylene (CyH,) and benzene (CH) have the same empirical formula, In fact, benzene can be made from acetylene as follows: 3CsHla(g) —> CoH ‘The enthalpies of combustion for CoH and CyH are 1299.4 kl/mol and ~3267.4 kI/mol, respectively. Calculate the standard enthalpies of formation of CM, and CH and hence the enthalpy change for the formation of CyH from CH, Tee at 0°C is placed in a Styrofoam cup containing 361 g of a soft drink at 23°C. The specific heat of the drink is about the same as that of water. Some jee remains after the ice and soft drink reach an ‘equilibrium temperature of 0°C, Determine the mass of ice that has melted. Ignore the heat capac- ity of the cup. (Hint: It takes 334.3 to melt lg of ice at 0°C.) ‘After dinner panty the host performed the following tick. First, he blew out one of the burning candles. He then quickly brought alighted match to about 1 in above the wick. To everyone's surprise, the candle was relighted. Explain how the host was able to-ac- ‘complish the task without touching the wick. How much heat is required to decompose 89.7 g of NELCI? (Hint: You may use the enthalpy of forma- tion values at 25°C for the ealeulation.) 6.129 6.130 6.131 6.132, 6.133 #6164 6.135 6.136 * 6.57 Questions & Problems 269 ‘A gas company in Massachusetts charges $1.30 for 15 ft of natural gas (CH,) messured at 20°C and 1.0 atm. Caleulate the cost of heating 200 mil of water (enough to make a cup of coffer or tes) from 20°C to 100°C. Assume that only 50 percent of the heat generated by the combustion is used to heat the ‘water; the rst of the heat is lost othe surroundings Calculate the intemal energy of a Goodyear blimp filled with helium gas at 1.2 % 10" Pa. The volume ofthe Bip is 5.5% 10" m?, If all he energy were used to eat 10.0 tons of copper at 21°, calculate the final temperature of the metal. (Hints See Sec- tion 57 for help in calculating the intemal energy of gas, Lon = 9.072 X 10° g) Decomposition reactions are usually endothermic, ‘whereas combination reactions are usually exother ric. Give a qualitative explanation for these trends Acetylene (C3H:) can be made by reacting cal- cium carbide (CaC;) with water. (a) Write an equation for the reaction. (b) What is the maxi ‘mum amount of heat (in joules) that can be ob- tained from the combustion of acetylene, starting with 74.6 g of CaC;? The average temperature in deserts is high during the day bat quite cool at night, whereas that in regions along the coastline is more moderate, Explain. ‘When 1.034 g of naphthalene (CoH) are burned in a constantvolume bomb calorimeter at 298 K, 41.36 KI of heat are evolved. Calculate AU and AH for the reaction on a molar basis. From a thermochemical point of view, explain why 4 carbon dioxide fie extinguisher or water should not be used on a magnesium fire CCaleulate the AU forthe following reaction 8298 K: 2HI(g) + Ox(g) —> 21,000 [Lime is a term that includes calcium oxide (CaO, also called quicklime) and calcium hydroxide [Ca(OH),, also called slaked lime}. It is used in the Steel industry to remove acidic impurities, in air- pollution control to remove acidic oxides such as SO;, and in water treatment. Quicklime is made in- ustrially by heating limestone (CaCOs) above 2000°C: CaCOs(s) —> CaO(s) + CO.) AP = 1778 kim Slaked lime is produced by treating quicklime with Ca0(s) + HO) —> Calls) AH? = 65.2 ki/mol ‘The exothermic reaction of quicklime with water and the rather small specific heats of both quicklime (0.946 Wg »*C) and slaked lime (1.20 Hg °C) make it ‘hazardous to Store and transport lime in vessels made of wood. Wooden sailing ships carrying lime would ‘occasionally catch fire when water leaked into the hold. (a) If a 500-g sample of water reacts with an270 Chapter 6+ Thermochemistry equimolar amount of CaO (both at an initial tempera- ture of 25°C), whats the final temperature of the prod- uct, Ca(OH);? Assume thatthe product absorbs all of the heat released in the reaction. (b) Given thatthe stan- ard enthalpies of formation of CaO and HO are =635.6 kifmol and =285 8 kimol, respectively, cal- culate te standard enthalpy of formation of Ca(OH), A 4.117-g impure sample of glucose (C,Hy,0.) was bbumed in @ constant-volume calorimeter having 2 hheat capacity of 19.654J/C. Lf the rise in temperature is 3.134°C, calculate the percent by mass ofthe glu- cose in the sample. Assume that the impurities are unaffected by the combustion process. See Appendix 3 for thermodynamic data, Construct a able withthe headings q, w, AU, and AH. For each of the following processes, deduce whether each of the quantities listed is positive (+), negative (©), or ze10 (0). (a) Freezing of benzene. (b) Compres- son ofan ideal gas at constant temperature. (c) Reac- tion of sodium with water. (4) Boiling liquid ammonia, (¢) Heating a gas at constant volume, (f) Melting of ie. ‘The combustion of 0.4196 g of @ hydrocarbon re- Teases 17.55 KI of heat. The masses of the products sare CO; = 1.419 g and H,O = 0.290 g. (a) What is the empirical formula of the compound? (b) If the approximate molar mass of the compound is 76 2 calculate its standard enthalpy of formation ‘Metabolic activity in the, human body releases approximately 1,0 X 10* KI of heat per day. Assuming the body is 50 kg of water, how much would the body temperature rise if it were an iso- lated system? How much water must the body climinate as perspiration to maintain the normal body temperature (98.6°F)? Comment on your re- sults, The heat of vaporization of water may be taken as 2.41 ki/g Give an example foreach ofthe following situations: (a) Adding heat to a system raises its temperature, (b) adding heat toa system does not change (ease) its Temperature, and (€) 2 system’s temperature is changed even though no heat is added or removed 6.138 6.139 6.140 6.41 6442 from it 6.143 From the following data, calculate the heat of solu tion for KE Nacl Nal KG Lattice energy 78 68RD (imo!) Hest of solution 4000-3100 1720 (arm) 6.144 Starting at A, an ideal gas undergoes a cyclic pro- cess involving expansion and compression, as shown here, Calculate the total work done. Does ‘your result support the notion that work is nota state function? ® 6.145 For reactions in condensed phases (liquids and solids), the difference between AH and AU is usu- ally quite small. This statement holds for reactions ccartied out under atmospheric conditions. For cer- tain geochemical processes, however, the external pressure may be so great that AH and AU can dif- fer by a significant amount. A well-known exam- ple is the slow conversion of graphite to diamond under Earth's surface, Calculate (AH — AU) for the conversion of I mole of graphite to | mole of iamond ata pressure of 50,000 atm, The densities of graphite and diamond are 2.25 g/em® and 3.52 g/em', respectively. 6146 Theta shone epee vos Ep pent era (b) MX(s) —> M*(ag) + X7(aq). (©) AB(e) + C(g) —> AC{g) + Big). (@) BQ —> Big). Pre- Se vaca ts Sn ae ss ary eet 8 eo'lle | lees oa o» |) $ lleo ® oll] |e! le® “@ @ 6147 A203 ample ofan enon mala 2h sample of copper, both at 80.6°C, are added to 100 g of water at 11.2°C in a constant-pressure calorimeter of negligible heat capacity. Ifthe final temperature of the metals and water is 13.7°C, determine the spe- cific heat of the unknown metal.