(BQ) Part 2 book Chemistry a molecular approach has contents: Chemical kinetics, chemical equilibrium, aqueous ionic equilibrium, free energy and thermodynamics, free energy and thermodynamics, organic chemistry, radioactivity and nuclear chemistry, chemistry of the nonmetals,...and other contents.
Exercises Sea Salts Seawater having a salinity of 35 g>kg contains 35 grams of NaCl per one kilogram of seawater Use the information provided in the figures to answer the following questions: a Calculate the freezing point of a sample of seawater having the highest salinity Calculate the freezing point of a sample of seawater having the lowest salinity Use a Van’t Hoff Factor of 1.9 in your calculation Assume the two samples contain water as the solvent and NaCl as the solute Chloride 55% (19.25g) Calcium 1.2% (0.42g) Potassium 1.1% (0.39g) Water 96.5% (965g) Sodium 30.6% (10.7g) Magnesium 3.7% (1.3g) Minor constituents 0.7% (0.25g) b Figure c▼ is a proposed graph of the freezing temperature of saltwater versus the amount of salinity A student claims that saltwater having a salinity of 280 g NaCl >kg of saltwater freezes at -20°C Is this claim accurate? Explain Salt 3.5% (35g) ▲ Figure a Cations and Anions in Ocean Water Figure b▼ illustrates the salinity of the oceans on Earth in grams of dissolved material (solute) per kilogram of seawater (solution) or parts per thousand (ppt) Freezing point (°C) Sulfate 7.7% (2.7g) 621 -5 -10 -15 -20 -25 Salinity (ppt) more than 37 37 36 35 34 less than 34 ▲ Figure b Salinity of Seawater in the Earth’s Oceans 100 200 Salinity (g/kg) 300 400 ▲ Figure c Salinity of Saltwater Versus the Freezing Point of Seawater c Use the information provided in Figure b and redraw the graph in Figure c using a range of salinity values from six different oceans The y-axis should be the freezing point of water, and the x-axis should be the salinity of seawater in units of grams of NaCl >kg of seawater Does Figure c provide an accurate view of the freezing point of the oceans? Because most of the dissolved minerals in seawater is sodium chloride, we can make the assumption that seawater Answers to Conceptual Connections Solubility 13.1 The first alcohol on the list is methanol, which is highly polar and temperature Therefore, the nitrogen becomes more soluble and will not bubble out of solution forms hydrogen bonds with water It is miscible in water and has only limited solubility in hexane, which is nonpolar However, as the carbon chain gets longer in the series of alcohols, the OH group becomes less important relative to the growing nonpolar carbon chain Therefore, the alcohols become progressively less soluble in water and more soluble in hexane This table demonstrates the rule of thumb like dissolves like Methanol is like water and therefore dissolves in water It is unlike hexane and therefore has limited solubility in hexane As you move down the list, the alcohols become increasingly like hexane and increasingly unlike water and therefore become increasingly soluble in hexane and increasingly insoluble in water Henry’s Law 13.4 Ammonia is the only compound on the list that is polar, so we Energetics of Aqueous Solution Formation 13.2 You can conclude that ΔHsolute ΔHhydration Since ΔHsoln is negative, the absolute value of the negative term (ΔHhydration) must be greater than the absolute value of the positive term (ΔHsolute) Solubility and Temperature 13.3 (b) Some potassium bromide precipitates out of solution The solubility of most solids decreases with decreasing temperature However, the solubility of gases increases with decreasing M13_TRO5187_04_SE_C13_570-621v4.0.6.indd 621 would expect its solubility in water to be greater than the solubilities of the other gases (which are all nonpolar) Molality 13.5 The solution has a molality of 10.0 m You combined 1.00 mol of solute with 0.100 kg of solvent, so the molality is 1.00 mol > 0.100 kg = 10.0 m Raoult’s Law 13.6 The solute–solvent interactions must be stronger than the solute–solute and solvent–solvent interactions The stronger interactions lower the vapor pressure from the expected ideal value of 150 mmHg Boiling Point Elevation 13.7 Solution B because Kb for ethanol is greater than Kb for water Colligative Properties 13.8 (c) The 0.50 M MgCl2 solution has the highest boiling point because it has the highest concentration of particles We expect mol of MgCl2 to form mol of particles in solution (although it effectively forms slightly fewer) 2015/11/24 7:43 PM C h a p ter 14 Chemical Kinetics Nobody, I suppose, could devote many years to the study of chemical kinetics without being deeply conscious of the fascination of time and change: this is something that goes outside science into poetry —Sir Cyril N Hinshelwood (1897–1967) 14.1 Catching Lizards 623 14.2 The Rate of a Chemical Reaction 624 14.3 The Rate Law: The Effect of Concentration on Reaction Rate 629 14.5 The Effect of Temperature on Reaction Rate 642 14.6 Reaction Mechanisms 648 14.7 Catalysis 653 K e y L e a r n i n g O u tcome s 6 14.4 The Integrated Rate Law: The Dependence of Concentration on Time 634 622 M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 622 2015/11/20 7:27 PM I n this chapter-opening quotation, Oxford chemistry professor Sir Cyril Hinshelwood calls attention to an aspect of chemistry often overlooked by the casual observer—the mystery of change with time Since the opening chapter of this book, you have learned that the goal of chemistry is to understand the macroscopic world by examining the molecular one In this chapter, we focus on understanding how this molecular world changes with time, an area of study called chemical kinetics The molecular world is anything but static Thermal energy produces constant molecular motion, causing molecules to repeatedly collide with one another In a tiny fraction of these collisions, something extraordinary happens—the electrons on one molecule or atom are attracted to the nuclei of another Some bonds weaken and new bonds form—a chemical reaction occurs Chemical kinetics is the study of how these kinds of changes occur in time ▲ Pouring ice water on a lizard slows it down, making it easier to catch 14.1 Catching Lizards The children who live in my neighborhood (including my own kids) have a unique way of catching lizards Armed with cups of ice water, they chase one of these cold-blooded reptiles into a corner, and take aim and pour the cold water directly onto the lizard’s body The lizard’s body temperature drops and it becomes virtually immobilized—easy prey for little hands The kids scoop up the lizard and place it in a tub filled with sand and leaves They then watch as the lizard warms back up and becomes active again They usually release the lizard back into the yard within hours I guess you could call them catch-and-release lizard hunters M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 623 623 2015/11/20 7:27 PM 624 Chapter 14 Chemical Kinetics A reaction with a fast rate A + B C 45 45 Unlike mammals, which actively regulate their body temperature through metabolic activity, lizards are ectotherms—their body temperature depends on their surroundings When splashed with cold water, a lizard’s body simply gets colder The drop in body temperature immobilizes the lizard because its movement depends on chemical reactions that occur within its muscles, and the rates of those reactions—how fast they occur—are highly sensitive to temperature In other words, when the temperature drops, the reactions that produce movement in the lizard occur more slowly; therefore, the movement itself slows down When reptiles get cold, they become lethargic, unable to move very quickly For this reason, reptiles try to maintain their body temperature within a narrow range by moving between sun and shade The rates of chemical reactions, and especially the ability to control those rates, are important not just in reptile movement but in many other phenomena as well For example, a successful rocket launch depends on the rate at which fuel burns—too quickly and the rocket can explode, too slowly and it will not leave the ground Chemists must always consider reaction rates when synthesizing compounds No matter how stable a compound might be, its synthesis is impossible if the rate at which it forms is too slow As we have seen with reptiles, reaction rates are important to life In fact, the human body’s ability to switch a specific reaction on or off at a specific time is achieved largely by controlling the rate of that reaction through the use of A reaction with a slow rate enzymes (biological molecules that we explore more fully in Section 14.7) X + Y Z The first person to measure the rate of a chemiTime ilhelmy (1812– cal reaction carefully was Ludwig W 1864) In 1850, he measured how fast sucrose, upon treatment with acid, hydrolyzed (broke up with the addition of water) into glucose and fructose This 15 reaction occurred over several hours, and Wilhelmy was able to show how the rate depended on the ini30 tial amount of sugar present—the greater the initial amount, the faster the initial rate Today we can measure the rates of reactions that occur in times as short as several femtoseconds (femto = 10 - 15) The knowledge of reaction rates is not only practically important—giving us the ability to control how fast a reaction occurs—but also theoretically important 15 As we will discuss in Section 14.6, the rate of a reaction can tell us much about how the reaction occurs 30 on the molecular scale 14.2 The Rate of a Chemical Reaction 45 15 The rate of a chemical reaction is a measure of how fast the reaction occurs, as shown in Figure 14.1◀ If a chemical reaction has a fast rate, a large fraction of molecules react to form products in a given period of time If a chemical reaction has a slow rate, only a relatively small fraction of molecules react to form products in a given period of time 15 Definition of Reaction Rate 30 45 30 ▲ Figure 14.1 The Rate of a Chemical Reaction M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 624 When we measure how fast something occurs, or more specifically the rate at which it occurs, we usually express the measurement as a change in some quantity per unit of time For example, we measure the speed of a car—the rate at which it travels—in miles per hour, and we measure how quickly (or slowly) people lose weight 2015/11/20 7:27 PM 625 14.2 The Rate of a Chemical Reaction in pounds per week We report these rates in units that represent the change in what we are measuring (distance or weight) divided by the change in time: Speed = change in distance change in time = ∆x ∆t Weight loss = change in weight change in time = ∆ weight ∆t Similarly, the rate of a chemical reaction is measured as a change in the amounts of reactants or products (usually in concentration units) divided by the change in time For example, consider the gas-phase reaction between H2( g) and I2( g): H2( g) + I2( g) ¡ HI( g) We can define the rate of this reaction in the time interval t1 to t2 as follows: Rate = - [H2]t2 - [H2]t1 ∆[H2] = [14.1] ∆t t2 - t1 In this expression, [H2]t2 is the hydrogen concentration at time t2 and [H2]t1 is the hydrogen concentration at time t1 The reaction rate is defined as the negative of the change in concentration of a reactant divided by the change in time The negative sign is part of the definition when we define the reaction rate with respect to a reactant because reactant concentrations decrease as a reaction proceeds; therefore, the change in the concentration of a reactant is negative The negative sign thus makes the overall rate positive (By convention, we report reaction rates as positive quantities.) Similarly, we can define the reaction rate with respect to the other reactant: Rate = - Recall that [A] means the concentration of A in M (mol >L) ∆[I2] [14.2] ∆t Since mol of H2 reacts with mol of I2, we define the rate in the same way We can also define the rate with respect to the product of the reaction: Rate = + ∆[HI] [14.3] ∆t Because product concentrations increase as the reaction proceeds, the change in concentration of a product is positive Therefore, when we define the rate with respect to a product, we not include a negative sign 1.8 in the definition—the rate is naturally posi- + The concentration of HI increases at twice the rate that the concentration of H2 or I2 decreases In other words, if 100 I2 molecules react per second, then 200 HI molecules form per second In order for the overall rate to have the same value when defined with respect to any of the reactants or products, we must multiply the change in HI concentration by a factor of one-half Consider the graph in Figure 14.2▶, which represents the changes in concentration for H2 (one of the reactants) and HI (the product) versus time Let’s examine several features of this graph individually M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 625 40 s 1.6 [HI] ∆t 1.4 Concentration (M) tive The factor of 12 in this definition is related to the stoichiometry of the reaction In order to have a single rate for the entire reaction, the definition of the rate with respect to each reactant and product must reflect the stoichiometric coefficients of the reaction For this particular reaction, mol of HI is produced from mol of H2 and mol of I2: 0.56 M 1.2 ∆[HI] [H2] H2(g) + I2(g) HI(g) 0.8 0.6 0.4 −0.28 M ∆[H2] 0.2 ∆t 40 s 0 20 40 60 Time (s) 80 100 120 ▲ Figure 14.2 Reactant and Product Concentrations as a Function of Time The graph shows the concentration of one of the reactants (H2) and the product (HI) as a function of time The other reactant (i2) is omitted for clarity 2015/11/20 7:27 PM 626 Chapter 14 Chemical Kinetics Change in Reactant and Product Concentrations The reactant concentration, as expected, decreases with time because reactants are consumed in a reaction The product concentration increases with time because products are formed in a reaction The increase in HI concentration occurs at exactly twice the rate of the decrease in H2 concentration because of the stoichiometry of the reaction: mol of HI form for every mol of H2 consumed The Average Rate of the Reaction We can calculate the average rate of the reaction for any time interval using Equation 14.1 for H2 The following table lists H2 concentration ([H2]) at various times, the change in H2 concentration for each interval (∆[H2]), the change in time for each interval (∆t), and the rate for each interval (- ∆[H2]> ∆t) The rate is the average rate within the given time interval For example, the average rate of the reaction in the time interval between 10 and 20 seconds is 0.0149 M>s, whereas the average rate in the time interval between 20 and 30 seconds is 0.0121 M>s Time (s) 0.000 1.000 10.000 0.819 20.000 0.670 30.000 0.549 40.000 0.449 50.000 0.368 60.000 0.301 70.000 0.247 80.000 0.202 90.000 0.165 100.000 𝚫[h2] (M) 𝚫t (s) Rate= − 𝚫[h2] , 𝚫t (M , s) V -0.181 10.000 0.0181 V -0.149 10.000 0.0149 V -0.121 10.000 0.0121 V -0.100 10.000 0.0100 -0.081 10.000 0.0081 -0.067 10.000 0.0067 -0.054 10.000 0.0054 -0.045 10.000 0.0045 -0.037 10.000 0.0037 -0.030 10.000 0.0030 [h2] (M) 0.135 V V V V V Notice that the average rate decreases as the reaction progresses In other words, the reaction slows down as it proceeds We discuss this further in the next section, where we will see that, for most reactions, the rate depends on the concentrations of the reactants As the reactants transform to products, their concentrations decrease, and the reaction slows down The Instantaneous Rate of the Reaction The instantaneous rate of the reaction is the rate at any one point in time and is represented by the instantaneous slope of the curve at that point We can determine the instantaneous rate by calculating the slope of the tangent to the curve at the point of interest In Figure 14.2, we have drawn the tangent lines for both [H2] and [HI] at 50 seconds We calculate the instantaneous rate at 50 seconds as follows: Using [H2] Instantaneous rate (at 50 s) = - ∆[H2] -0.28 M = = 0.0070 M>s ∆t 40 s Using [HI] Instantaneous rate (at 50 s) = + ∆[HI] 0.56 M = + = 0.0070 M>s ∆t 40 s As we would expect, the rate is the same whether we use one of the reactants or the product for the calculation Notice that the instantaneous rate at 50 seconds (0.0070 M>s) is between the average rates calculated for the 10-second intervals just before and just after 50 seconds M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 626 2015/11/20 7:27 PM 14.2 The Rate of a Chemical Reaction 627 We can generalize our definition of reaction rate for the generic reaction: aA + bB ¡ cC + dD[14.4] where A and B are reactants, C and D are products, and a, b, c, and d are the stoichiometric coefficients We define the rate of the reaction as follows: Rate = - ∆[A] ∆[B] ∆[C] ∆[D] [14.5] = = + = + a ∆t b ∆t c ∆t d ∆t From the definition, we can see that knowing the rate of change in the concentration of any one reactant or product at a point in time allows us to determine the rate of change in the concentration of any other reactant or product at that point in time (from the balanced equation) However, predicting the rate at some future time is not possible from just the balanced equation Example 14.1 Expressing Reaction Rates Consider this balanced chemical equation: H2O2(aq) + I - (aq) + H + (aq) ¡ I3 - (aq) + H2O(l ) In the first 10.0 seconds of the reaction, the concentration of I - drops from 1.000 M to 0.868 M (a) Calculate the average rate of this reaction in this time interval (b) Determine the rate of change in the concentration of H + (that is, ∆[H + ]> ∆t) during this time interval Solution (a) Use Equation 14.5 to calculate the average rate of the reaction Rate = = - (b) Use Equation 14.5 again for the relationship between the rate of the reaction and ∆[H + ]> ∆t After solving for ∆[H + ]> ∆t, substitute the calculated rate from part (a) and calculate ∆[H + ]> ∆t ∆[I - ] ∆t (0.868 M - 1.000 M) 10.0 s = 4.40 * 10 -3 M > s Rate = - ∆[H + ] ∆t ∆[H + ] = -2(rate) ∆t = -2(4.40 * 10 - M>s) = -8.80 * 10 - M>s For Practice 14.1 For the reaction shown in Example 14.1, predict the rate of change in concentration of H2O2 (∆[H2O2]> ∆t) and I3 - (∆[I3 - ]> ∆t) during this time interval Reaction Rates For the reaction A + 2B ¡ C under a given set of conditions, the initial rate is 0.100 M>s What is ∆[B]> ∆t under the same conditions? (b) -0.100 M>s (c) -0.200 M>s (a) -0.0500 M>s C o nc e p t u a l Connection 14.1 Measuring Reaction Rates In order to study the kinetics of a reaction, we must have an experimental way to measure the concentration of at least one of the reactants or products as a function of time For example, Ludwig Wilhelmy, whose experiment on the rate of the conversion of M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 627 2015/11/20 7:27 PM 628 Chapter 14 Chemical Kinetics sucrose to glucose and fructose we discussed briefly in Section 14.1, took advantage of sucrose’s ability to rotate polarized light (Polarized light is light with an electric field oriented along one plane.) When a beam of polarized light is passed through a sucrose solution, the polarization of the light is rotated clockwise In contrast, the products of the reaction (glucose and fructose) rotate polarized light counterclockwise By measuring the degree of polarization of light passing through a reacting solution—a technique known as polarimetry—Wilhelmy was able to determine the relative concentrations of the reactants and products as a function of time Perhaps the most common way to study the kinetics of a reaction is through spectroscopy (see Section 7.3) For example, the reaction of H2 and I2 to form HI can be followed spectroscopically because I2 is violet and H2 and HI are colorless As I2 reacts with H2 to form HI, the violet color of the reaction mixture fades We can monitor the fading color with a spectrometer, a device that passes light through a sample and measures how strongly the light is absorbed (Figure 14.3▼) If the sample contains the reacting mixture, the intensity of the light absorption will decrease as the reaction proceeds, providing a direct measure of the concentration of I2 as a function of time Because light travels so fast and because experimental techniques can produce very short pulses of light, spectroscopy can be used to measure reactions that happen on time scales as short as several femtoseconds ▼ Figure 14.3 The Spectrometer In a spectrometer, light of a specific wavelength is passed through the sample, and the intensity of the transmitted light—which depends on how much light is absorbed by the sample—is measured and recorded Source Slit Monochromator Sample Detector Computer By measuring changes in pressure, we can also monitor reactions in which the number of moles of gaseous reactants and products changes as the reaction proceeds Consider the reaction in which dinitrogen monoxide reacts to form nitrogen and oxygen gas: Aliquot N2O( g) ¡ N2( g) + O2( g) Injection port Detector Chromatogram Column Carrier gas supply Oven ▲ Figure 14.4 The Gas Chromatograph In a gas chromatograph (GC), a sample of the reaction mixture, or aliquot, is injected into a specially constructed column Because of their characteristic physical and chemical properties, different components of the mixture pass through the column at different rates and thus exit at different times As each component leaves the column, it is detected electronically and a chromatogram is recorded The area under each peak in the chromatogram is proportional to the amount of one particular component in the sample mixture M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 628 For every mol of N2O that reacts, the reaction vessel contains one additional mole of gas As the reaction proceeds and the amount of gas increases, the pressure steadily rises We can use the rise in pressure to determine the relative concentrations of reactants and products as a function of time We can use all of the three techniques mentioned here—polarimetry, spectroscopy, and pressure measurement—to monitor a reaction as it occurs in a reaction vessel Some reactions occur slowly enough that samples, or aliquots, can be periodically withdrawn from the reaction vessel and analyzed to determine the progress of the reaction We can use instrumental techniques such as gas chromatography (Figure 14.4◀) or mass spectrometry, as well as wet chemical techniques such as titration, to measure the relative amounts of reactants or products in the aliquot By taking aliquots at regular time intervals, we can determine the relative amounts of reactants and products as a function of time 2015/11/20 7:27 PM 14.3 The Rate Law: The Effect of Concentration on Reaction Rate 14.3 The Rate Law: The Effect of Concentration on Reaction Rate 629 The Rate Law for a Chemical Reaction The rate of a reaction often depends on the concentration of one or more of the reactants As we have already seen, Ludwig Wilhelmy noticed this effect for the hydrolysis of sucrose For simplicity, let’s consider a reaction in which a single reactant, A, decomposes into products: A ¡ products As long as the rate of the reverse reaction (in which the products return to reactants) is negligibly slow, we can express the relationship between the rate of the reaction and the concentration of the reactant—called the rate law—as follows: Rate = k[A]n [14.6] where k is a constant of proportionality called the rate constant and n is the reaction order The value of n (usually an integer) determines how the rate depends on the concentration of the reactant: • If n = 0, the reaction is zero order and the rate is independent of the concentration of A By definition, [A]0 = 1, so the rate is equal to k regardless of [A] • If n = 1, the reaction is first order and the rate is directly proportional to the concentration of A • If n = 2, the reaction is second order and the rate is proportional to the square of the concentration of A Although other orders are possible, including noninteger (or fractional) orders, these three are the most common The Three Common Reaction Orders (n = 0, 1, and 2) Figure 14.5▼ shows three plots illustrating how the concentration of A changes with time for the three common reaction orders with identical numerical values for the rate constant (k) and identical initial concentrations Figure 14.6▼ has three plots showing the rate of the reaction (the slope of the lines in Figure 14.5) as a function of the reactant concentration for each reaction order Rate versus Reactant Concentration Reactant Concentration versus Time 0.018 0.016 0.8 0.6 Rate (M/s) 0.014 [A] Second order n =2 0.4 0.012 0.010 First order Rate = k[A]1 0.008 0.006 0.2 Zero order Rate = k[A]0 Zero order n =0 20 40 First order n =1 100 ▲ Figure 14.5 Reactant Concentration as a Function of Time for Different Reaction Orders M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 629 0.002 60 80 Time (s) Second order Rate = k[A]2 0.004 120 0.2 0.4 [A] 0.6 0.8 ▲ Figure 14.6 Reaction Rate as a Function of Reactant Concentration for Different Reaction Orders 2015/11/20 7:27 PM 630 Chapter 14 Chemical Kinetics Sublimation Is Zero Order Ice in glass tube Zero-Order Reaction In a zero-order reaction, the rate of the reaction is independent of the concentration of the reactant: Rate = k[A]0 = k[14.7] Consequently, for a zero-order reaction, the concentration of the reactant decreases linearly with time, as shown in Figure 14.5 The slope of the line is constant, indicating a constant rate The rate is constant because the reaction does not slow down as the concentration of A decreases The graph in Figure 14.6 shows that the rate of a zero-order reaction is the same at any concentration of A Zero-order reactions occur under conditions where the amount of reactant actually available for reaction is unaffected by changes in the overall quantity of reactant For example, sublimation is normally zero order because only molecules at the surface of a substance can sublime, and the concentration of the surface molecules does not change as the amount of subliming substance decreases (Figure 14.7◀) First-Order Reaction When one layer of particles sublimes, the next layer is exposed The number of particles available to sublime remains constant ▲ Figure 14.7 Sublimation When a layer of particles sublimes, another identical layer is just below it Consequently, the number of particles available to sublime at any one time does not change with the total number of particles in the sample, and the process is zero order In a first-order reaction, the rate of the reaction is directly proportional to the concentration of the reactant: Rate = k[A]1[14.8] For a first-order reaction, the rate slows down as the reaction proceeds because the concentration of the reactant decreases We can see this in Figure 14.5—the slope of the curve (the rate) becomes less steep (slower) with time Figure 14.6 shows the rate as a function of the concentration of A Notice the linear relationship—the rate is directly proportional to the concentration Second-Order Reaction In a second-order reaction, the rate of the reaction is proportional to the square of the concentration of the reactant: Rate = k[A]2[14.9] Consequently, for a second-order reaction, the rate is even more sensitive to the reactant concentration We can see this in Figure 14.5—the slope of the curve (the rate) flattens out more quickly than it does for a first-order reaction Figure 14.6 shows the rate as a function of the concentration of A Notice the quadratic relationship—the rate is proportional to the square of the concentration Determining the Order of a Reaction The order of a reaction can be determined only by experiment A common way to determine reaction order is the method of initial rates In this method, the initial rate—the rate for a short period of time at the beginning of the reaction—is measured by running the reaction several times with different initial reactant concentrations to determine the effect of the concentration on the rate For example, let’s return to our simple reaction in which a single reactant, A, decomposes into products: A ¡ products In an experiment, the initial rate is measured at several different initial concentrations with the following results: [A] (M) M14_TRO5187_04_SE_C14_622-673v3.0.8.indd 630 Initial Rate (M , s) 0.10 0.015 0.20 0.030 0.40 0.060 2015/11/20 7:27 PM I-18 Index Nonmetal(s) (cont.) bonds, types of, 1065 carbides, 1073–1075 carbonates, 1075–1076 carbon oxides, 1075 electron affinities of, 385 insulated nanowires, 1063–1064 ion formation by, 64 ionization energies of, 385 reactions of alkali metals with, 371 silicates, 1065–1069 Nonoxide ceramics, 554 Nonpolar bonds, 440 Nonpolar covalent bonds, 398 Nonpolar solvents, 576 Nonspontaneous processes, 841–843, 853, 856, 867 Nonstandard states, free energy changes for, 870–873 Nonstoichiometric compounds, 567 Nonvolatile liquids, 503 Normal boiling point, 508 Normalization, of total intensity, 67 Normal science, Novoselov, Konstantin, 533, 534 n-type semiconductors, 557 Nuclear binding energy, 960–962 Nuclear charge, 342, 352–356 Nuclear chemistry, 956–967 See also Radioactivity effects of radiation on life, 964–967 fission, 956–959 fusion, 60, 962–963 mass defect and nuclear binding energy, 960–962 transmutation and transuranium elements, 963–964 Nuclear energy industry, 1070, 1092 Nuclear equation(s), 942–944, 956 Nuclear fission, 956–962 Nuclear fusion, 60, 962–963 Nuclear medicine, 939–940 Nuclear power, 958–959 Nuclear power plants, 958–959 Nuclear reactors, 958 Nuclear stability, 946–948 Nuclear theory of atom, 54–55 Nuclear transmutation, 963–964 Nuclear waste, disposal of, 959 Nuclear weapons, 956–958 Nucleic acids, 69, 1046–1049 Nucleon(s), 946–948, 961, 962 Nucleotide(s), 498, 1046–1049, 1060 Nucleus(–i), 54, 939 in metastable state, 943–944 strong force binding, 946–947 Nuclide(s), 941, 942, 950, 961, 962 Nylon 6,6, 559, 560 Nyos, Lake, 586 N/Z ratio, 946–947 O Obama, Barack, 959 Observation, Octahedral complexes cis–trans isomerism in, 1139–1140 d orbital energy changes for, 1143 fac–mer isomerism in, 1140 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 18 high-spin, 1146–1147 low-spin, 1146–1147 optical isomerism in, 1141–1142 Octahedral geometry of complex ions, 1135 electron, 435, 436, 458 molecular, 431, 436, 439, 457 Octahedral hole, 1112 Octane, 135, 141–145, 501, 988, 989 Octaves, 338 Octet(s), 386–387 expanded, 407, 410–411, 456 incomplete, 407–410 Octet rule, 387, 396, 407–411 Odd-electron species, 407, 408 Odors, 979–980, 1007–1008, 1010 See also Aromatic hydrocarbons OH- See Hydroxide ion; Hydroxide ion concentration OH- functional group, 125 Oil(s), 501, 503, 1032–1033, 1101–1102 Oil drop experiment, Millikan’s, 52–53 Oleic acid, 1031, 1032 Oleum, 1089 Olfaction, 979 Oligopeptides, 1041 Olivines, 1067 On the Revolution of the Heavenly Orbs (Copernicus), 47 Opal, 609 Opaque, metals as, 1102 Operators, algebraic, 317 Oppenheimer, J R., 958 Optical isomerism, 985–987, 1036, 1140–1142 Orbital angular momentum, 469 Orbital diagram, 340 Orbital overlap See Valence bond theory Orbitals, 317 See also Atomic orbitals; Molecular orbitals Order of magnitude estimations, 31–32 Ores, 1103–1108 Organic bases, 498–499 Organic chemistry, 65, 978–1027 See also Hydrocarbons alcohols, 1004–1006 aldehydes, 1006–1009 alkanes, 988–992 alkenes and alkynes, 992–997 amines, 1012 carboxylic acids, 1009–1011 esters, 1009–1011 ethers, 1011–1012 fragrances and odors, 979–980 functional groups, 1003 ketones, 1006–1009 and uniqueness of carbon, 979, 980–982 Organic compound(s), 123–126, 406–407, 981 Organic molecules, 980 Orientation factor, 647–648 Orthorhombic unit cells, 537 Orthosilicates (nesosilicates), 1067, 1069 Osmosis, 603, 607 Osmosis cell, 603–604 Osmotic pressure, 603–605 Osteoporosis, 20 Ostwald process, 1080 Outer electron configuration, 349 Outermost electrons, 355 Overvoltage, electrolysis of aqueous sodium chloride and, 922–923 Oxalate ion, 1133 Oxalic acid, ionization constants for, 758 Oxidation defined, 175, 890 selective, 905 Oxidation–reduction reaction(s), 175–182 of alcohols, 1005, 1008 in aqueous solutions, balancing, 890–893 in batteries, 914–918 combustion reactions, 181–182 corrosion as undesirable, 926–927 fuel cells based on, 890 generating electricity from, 893–897 identifying, 178–181 with oxygen, 175 with partial electron transfer, 176 spontaneous direction of, 902–905, 907 without oxygen, 175, 176 Oxidation state(s) (oxidation number(s)), 176–178, 890 of halogens in compounds, 1089 identifying changes in, 1093 identifying redox reactions from, 178–181 of nitrogen compounds, 1078 of polyatomic ions, 178 rules for assigning, 177–178 in sulfur reactions, 1087 of transition metals, 1131 Oxide(s), 98, 1084 See also specific compounds halogen, 1092–1093 nitrogen, 765–766, 1079–1080 phosphorus, 1081–1082 sulfur, 765–767 Oxide ceramics, 554 Oxide minerals, 1103 Oxidizing agents, 179, 180, 901, 1065, 1084, 1115 Oxyacids (oxoacids), 104–105, 763 Oxyanions, 100, 101 Oxygen, 1083–1085 See also Ozone in air, 214, 215 boron–oxygen compounds, 1071 chemistry of life and, 65 in combustion reactions, 181–182 electron configuration for, 345 elemental, 1083–1084 emission spectrum of, 310 Henry’s law constants for, 584 ionization energy of, 364 Lewis structure of, 386, 394 liquid, 469 orbital diagram for, 345, 467–469 oxidation state for, 177 as oxidizing agent, 179 and oxyacid strength, 763 paramagnetism of, 469 partial pressure limits of, 217 properties of, 57, 62, 87–89 reaction between xenon and, 372 redox reactions with, 175 redox reactions without, 176 2015/11/20 9:28 PM in silicate tetrahedron, 1066 uses for, 1084 van der Waals constants for, 233 ∆H°f for compounds containing, 276 Oxygen toxicity, 217, 616 Oxygen transport, 1102 Ozone from combustion of fossil fuels, 282 decomposition of, 409, 653–656 from fuel fragments in e xhaust, 655 Lewis structure of, 416, 472 molecular orbital model of, 472 properties of, 38 resonance hybrid structure of, 403 use of, 1084–1085 valence bond model of, 472 Ozone layer, 634, 1085 P P (Poise), 501 ∆P (vapor pressure lowering), 593–596 Pa (Pascal), 199, 200 Packing efficiency, 538–541 Palmitic acid, 292, 1031 Parabolic troughs, 284 Paramagnetism, 357–358, 469, 1146 Parent nuclide, 942 Partially hydrogenated vegetable oil, 998 Partial pressures, 214–221 and collecting gases over water, 219–221 Dalton’s law of, 215–217, 225–226 deep-sea diving and, 217–218 and equilibrium constant, 684–685 finding equilibrium, 698–699 free energy change of reaction with, 872 Particle nature of light, 305–308 Parts by mass, 587–589 Parts by volume, 587–589 Parts per billion by mass (ppb), 587, 588 Parts per million by mass (ppm), 587, 588 Pascal (Pa), 199, 200 Patchouli alcohol, 979, 980 Patina, 1117 Pauli, Wolfgang, 340 Pauli exclusion principle, 340–341, 344 Pauling, Linus, 138, 397 Pc (critical pressure), 512 PCBs (polychlorinated biphenyls), 590 Peaches, pH of, 734 Penetrating power, 943, 944 Penetration, 342 Pentaamminebromocobalt(II), 1137 Pentaamminechlorocobalt(II), 1137 Pentaamminenitritocobalt(III), 1138 Pentaamminenitrocobalt(III), 1138 Pentagonal bipyramidal geometry, 1092 Pentanal, 1007 Pentane, 291 common uses of, 125 critical point transition for, 511–512 dynamic equilibrium in, 506–507 formula of, 125, 988 intermolecular forces in, 575 miscibility of water and, 494 molecular formula for, 125 neopentane vs., 491, 492 space-filling model of, 125 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 19 Index structure of, 983 viscosity of, 501 Pentanoic acid, 1009 Pentanol, 577 2-Pentanone, 1007 1-Pentene, 993 1-Pentyne, 994 Peptide bond(s), 658, 1041–1042 Percent by mass (%), 587, 588 Percent ionic character, 399 Percent ionization, of weak acid, 742–743 Percent mass to volume, 608 Percent yield, 146–148 Perchlorate, 100, 101 Perchloric acid, 169, 729 Peridot, 1128 Period elements, 465–472 Periodic law, 61, 62, 339 Periodic property(-ies), 336–381 of alkali metals (group 1A), 369–371 defined, 338 and development of periodic table, 338–339 effective nuclear charge and, 352–356 electron affinities, 365–366 electron configurations and, 339–351, 357–358 of halogens, 370–371 of ions, 357–365 of main-group elements, 1064–1065 metallic character, 366–368 nerve signal transmission and, 337–338 of noble gases, 371–372 and quantum-mechanical model, 351–352 sizes of atoms, 352–356 transition elements and, 355–356 Periodic table, 60–65, 337, 1065 See also specific elements; specific families or groups atomic mass, 65–66 development of, 338–339 ions and, 64–65 modern, 62–64 orbital blocks in, 348–349 organization of, 57 quantum-mechanical theory and, 337, 339–351 writing electron configuration from, 349–350 Permanent dipoles, 492 Permanganate, 100 Permanganate ion, 1116 Peroxide, 100, 1084 Perpetual motion machine, 253, 840 Perrin, Jean, 46, 47 Persistent organic pollutants (POPs), 590 Perturbation theory, 445 PET (positron emission tomography), 968 Peta prefix, 17 Petroleum, 280, 281 pH See also Acid–base chemistry; Buffers of blood, 780, 794 of buffers, 782–783 of mixture of acids, 743–745 of polyprotic acids, 758–760 of salt solutions, 755–757 solubility and, 814 I-19 of solution with anion acting as weak base, 752–754 of solution with conjugate acid of weak base, 755 of strong acid solutions, 737 of weak acid solutions, 737–741 of weak bases, 748–749 Phase(s) of matter, 486–489 See also Gas(es); Liquid(s); Solid(s) of orbitals, 327–328 of waves, 303 Phase diagram(s), 517–520, 1109–1111 Phase transition(s), 488–489 condensation, 503, 504, 852, 1010–1012 critical point, 511–512 deposition, 513 entropy and, 848–852 freezing, 513–514, 521 melting or fusion, 513–514 sublimation, 11, 512–514, 630 vaporization, 502–512, 514 pH curves, 795–806 Phenol, 731, 1000, 1001 Phenolphthalein, 807, 809 Phenol red, 809 4-Phenyl-1-hexene, 1001 Phenylalanine, 1039, 1040 Phenyl group, 1001 3-Phenylheptane, 1001 pH meters, 806 Phosgene (carbonyl chloride), 423, 671, 1075 Phosphate(s), 100, 820, 1082–1083 Phosphate links, in nucleic acids, 1048 Phosphatidylcholine, 1033, 1034 Phosphide, 98 Phosphine, 1081 Phospholipids, 1033, 1034 Phosphorescence, 940 Phosphoric acid, 724, 730, 758, 1082 Phosphorus, 1076 black, 1077 compounds, 1081–1083 elemental, 1077 ionization energies of, 365 as molecular element, 94 red, 1077 silicon doped with, 557 white, 1077, 1081–1082 Phosphorus-30, 944 Phosphorus-32, 967, 968 Phosphorus halides, 1081 Phosphorus oxides, 1081–1082 Phosphorus oxychloride, 1081 Phosphorus oxyhalides, 1081 Phosphorus pentachloride, 431 Photochemical smog, 282 Photoelectric effect, 305–308 Photons, 306–307, 321 Photosynthesis, 291, 1075, 1083, 1148, 1150 pH scale, 723, 734–735 Phyllosilicates, 1068–1069 Physical changes, 9–12 Physical property, 10 Physics, classical, 315–316 p*2p antibonding orbital, 466, 467 p2p bonding orbital, 466, 467 2015/11/20 9:28 PM I-20 Index Pi (p) bonds, 452 Pico prefix, 17 PIR mnemonic, 903, 921 pKa scale, 736 Planck, Max, 297, 306 Planck’s constant, 306 Plane-polarized light, 986–987 Plastic(s), 533, 557–560 Platinum, 19, 897 Plato, 3, 47 Plum-pudding model, 53, 54 Plums, pH of, 734 p-n junctions, 557 pOH scale, 735–736 Poise (P), 501 Polar bonds, 394–396, 398–400, 440–444, 762 Polar covalent bonds, 396 Polarimetry, 628 Polarity bond, 394–396, 398–400, 762 molecular shape and, 440–444 Polarized light, 628, 986–987 Polar molecules, 493–494 Polar solvents, 576 Polar stratospheric clouds (PSCs), 655 Pollutant(s), 104, 590, 1088 Pollution, 281–282, 521, 654–655 Polonium, 57, 941 Polyatomic ion(s), 95, 100–101 balancing equations with, 122–123 Lewis structures for, 400, 402 oxidation numbers in, 178 Polyatomic molecules, 94, 472–473 Polychlorinated biphenyls (PCBs), 590 Polycyclic aromatic hydrocarbons, 1001–1002 Polydentate ligands, 1134 Polyethylene, 558, 559 Polyethylene terephthalate, 559 Polymer(s), 557–560, 1030 Polymorphism, 546 Polypeptides, 1041 Polypropylene, 559 Polyprotic acids, 168, 757–761 acid ionization constants for, 757–758 concentration of anions for weak diprotic acid s olution, 760–761 dissociation of, 761 ionization of, 757–758 pH of, 758–760 titration of, 805–806 Polysaccharides, 1037–1038 Polystyrene, 559 Polyunsaturated fatty acids, 1031 Polyurethane, 559 Polyvinyl chloride (PVC), 558, 559 Popper, Karl, 382, 383 POPs (persistent organic pollutants), 590 p orbitals, 319, 326 2p, 326, 328, 342–343 and properties of main-group elements, 1065–1066 Porphyrin, 1127, 1148, 1149 Portland cement, 554–555 Position in classical mechanics, 315–316 and energy as complementary properties, 317 and potential energy, 250 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 20 and velocity as complementary properties, 317 Positron, 944 Positron emission, 941, 944, 945 Positron emission tomography (PET), 968 Potassium, 63 flame tests for, 311 Lewis structure of, 387 properties of, 369–370 reaction between bromine and, 648 reaction between chlorine and, 387 Potassium bromide, 755 Potassium chloride, 96, 98, 391, 1103 Potassium hydroxide, 169, 170, 580, 726, 746 Potassium iodide, 64, 162–164, 393, 816 Potassium ions, 337–338, 914 Potassium nitrate, 582–583 Potassium nitrite, 755 Potassium permanganate, 393 Potato cannon, 258 Potential difference, 895–896, 906 Potential energy of charged particles, 384, 385–386 Coulomb’s law and, 489 defined, 12, 250 exothermic chemical reactions and, 269 and law of conservation of energy, 13 solution formation and, 574 stability of covalent bond and, 90 transformation of, 251 Pounds per square inch (psi), 199 Powder metallurgy, 1107–1108 Power, units raised to, 30 Power grid, 889–890 Power plants, fuel-cell, 890 ppb (parts per billion by mass), 587, 588 ppm (parts per million by mass), 587, 588 Precipitate, 162 Precipitation (precipitation reactions), 162–166, 815–820 qualitative analysis by, 818–820 reaction quotient and, 815–816 selective, 816–818 from supersaturated solution, 582 writing equations for, 165–166 Precision, 22, 25–26 Pre-exponential factor See Frequency factor (A) Prefixes, 17, 101, 102, 990 Pressure(s), 198–201 See also Gas(es); Partial pressures blood, 201 calculating, 226–227 critical, 512 defined, 198 dynamic equilibrium and, 506 equilibrium constant in terms of, 685–686 free energy for water vs., 871 gas amount and, 223 gas solubility in water and, 583–585 gauge, 210, 241 heat in reactions at constant, 267–270 kinetic molecular theory and, 225–226 Le Châtelier’s principle on change in, 706–707 manometer to measure, 200–201 molecular collisions and, 198–199 osmotic, 603–605 particle density and, 198 phase changes and, 488 and reaction rates, 628 SI unit of, 199–200 STP, 211–212 temperature and, 209 total, 210, 216–217 units of, 199–200 vapor, 219, 505–511, 597–599, 606–607 volume and, 202–204 Pressure–volume work, 262–264 Priestley, Joseph, 1083 Primary structure, protein, 1043, 1044, 1046 Primary valence, 1132 Principal level (principal shell), 319 Principal quantum numbers (n), 317, 318, 362 Principles, Probability density, 323–325 Probability distribution maps, 315–317 Problem solving, 26–33 Product(s) in balanced chemical equations, 119, 120 concentration of, 625–626 and law of conservation of mass, 47 in stoichiometry, 139 Proline, 1040 Proof, of alcoholic beverages, 1004 Propanal, 1007 Propane burning of, 11 combustion of, 269–270 common uses of, 125 formation of, 998 formula of, 125, 988 ionic compounds vs., 94 liquid, 488 space-filling model of, 125 structure of, 124, 981 Propanoic acid, 1009, 1010 2-Propanol See Isopropyl alcohol Propanone See Acetone 2-Propanone, 1008 Propene, 984, 993, 998, 999 Property(-ies) extensive and intensive, 18 periodic See Periodic property(-ies) physical, 10 Propylene glycol, 779 Propyl substituent, 990 Propyne, 984, 994 Protactinium-234, 948 Protease inhibitors, 384 Protective proteins, 1038 Protein(s), 383–384, 1038–1049 See also Amino acids defined, 1030 digestion of, 658 fibrous, 1042–1043 functions, 1038 globular, 1043 mass spectrum of, 69 monomeric, 1046 multimeric, 1046 nucleic acids as blueprints for, 1046–1049 structure of, 1042–1046 synthesis of, 1051 T1r3, 428 2015/11/20 9:28 PM Proton(s), 40, 54 actual number of, 947–948 Brønsted–Lowry definition of acids and bases and, 727–728, 762, 764 charge of, 55, 56 ionizable, 729 mass of, 55, 56 number of, in elements, 56–57 N/Z ratio and, 946–947 repulsive electrostatic force among, 946 symbol for, 941 Proust, Joseph, 48, 49 PSCs (polar stratospheric clouds), 655 Pseudogout, 834 psi (pounds per square inch), 199 c (wave function), 317 p-type semiconductors, 557 Pumps, ion, 337–338 Pure compounds, 275 Pure substances, 7, Purine bases, 1047–1048 PVC (polyvinyl chloride), 558, 559 Pyrene, 1002 Pyrex®, 259, 555 Pyridine, 747 Pyrimidine bases, 1047–1048 Pyrolusite, 1115–1116 Pyrometallurgy, 1104–1105 Pyrosilicates (sorosilicates), 1067, 1069 Pyroxenes (inosilicates), 1067–1069 Q Q (reaction quotient), 691–693, 815–816 Quadratic equations, 695 Qualitative analysis, 818 Qualitative chemical analysis, 818–820 Quantitative analysis, 818 Quantized energy, 310 Quantum, of light, 306–307 Quantum-mechanical model of atom, 296–335 and atomic spectroscopy, 320–323 atomic spectroscopy and Bohr model, 308–311 explanatory power of, 351–352 nature of light, 298–308 nodes and wave functions, 326 periodic table and, 337, 339–351 Schrödinger equation for hydrogen atom, 317–320 Schrödinger’s cat and, 297–298 shapes of atomic orbitals, 323–328 wave nature of matter and, 311–317 Quantum-mechanical strike zone, 317 Quantum mechanics, 62 Quantum numbers, 317–320, 340–341 Quarks, 964 Quartz, 545, 553, 1066 Quaternary structure, protein, 1043, 1046 R Racemic mixture, 986 Radial distribution functions, 324–326, 343 Radiation in cancer treatment, 303 electromagnetic, 299–300 See also Light of hydrogen energy, 320–323 ionizing, 303 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 21 Index Radiation dose, 965–967 Radiation exposure, 964–967 Radicals, 409, 423, 998 Radioactive atoms, 940 Radioactive decay, 949–955 Radioactive decay series, 948 Radioactivity, 939–955 See also Nuclear chemistry defined, 940 detecting, 948–949 discovery of, 53, 940–941 kinetics of radioactive decay and radiometric dating, 949–955 in medicine, 939–940, 967–969 other applications, 969 types of, 941–946 and valley of stability, 946–948 Radiometric dating, 952–955 Radiotherapy, 968–969 Radiotracers, 967–968 Radio waves, 302 Radium, 941, 1103 Radium-228, 943 Radon-220, 950 Rain, acid, 104, 143–144, 281, 765–767, 1088 Rainwater, pH of, 734 Rana sylvatica (wood frogs), 603 Random coils, 1045 Random errors, 26 Raoult, Franỗois-Marie, 570 Raoults law, 595599 Rapture of the deep (nitrogen narcosis), 217, 616 Rate constant(s) (k), 629, 631, 642 Rate-determining steps, 650–651 Rate law, 629–634 containing intermediates, 652 determining order of reaction, 630–633 differential, 635 for elementary steps, 649–650 first-order reaction, 629, 630, 641 integrated, 634–641, 951–952 overall, 650–651 reaction order for multiple reactants, 632–634 second-order reaction, 629–631, 641 zero-order reaction, 629–631, 641 RBE (biological effectiveness factor), 966 Reactant(s) in balanced chemical equations, 119, 120 concentration of, 625–626 in excess, 151 and law of conservation of mass, 47 limiting, 145–151 reaction order for multiple, 632–634 in stoichiometry, 139 Reaction(s), 119, 138–195 See also Free energy change of reaction (∆G); specific types of alcohols, 1004–1006 of aldehydes and ketones, 1008–1009 of amines, 1012 of aromatic hydrocarbons, 1002 of carboxylic acids and esters, 1010–1011 chemical quantities in, 138–151 direction of, 691–693 enthalpy changes for, 269–280, 413–414 entropy changes in, 859–863 I-21 gases in, 221–223 half-life of, 638–641, 949–950 heat evolved in, at constant pressure, 267–270 of hydrocarbons, 997–999 internal energy change for, 264–266 rates of See Reaction rate(s) spontaneity of, 841–843 standard enthalpy change for, 277–280, 864–865 standard entropy change for, 859–865 Reaction coefficients, and stoichiometry, 141 Reaction intermediates, 649, 652 Reaction mechanisms, 648–653 Reaction order (n), 629–634 Reaction quotient (Q), 691–693, 815–816 Reaction rate(s), 622–673 average, 626 catalysis, 653–658 defined, 624–627 instantaneous, 626–627 integrated rate law, 634–641 measuring, 627–628 of radioactive decay and radiometric dating, 949–955 rate law, 629–634, 650–651 and reactant/product c oncentrations, 626 reaction mechanisms and, 648–653 in reptile movement, 623–624 temperature effect on, 642–648 thermodynamics and, 842, 843 Reaction stoichiometry, 141–145 enthalpy change and, 269–270 for gases, 221–223 limiting reactant, 145–151 mass-to-mass conversions, 142–143 mole-to-mole conversions, 141–142 percent yield, 146–148 theoretical yield, 145–151 Reactivity, of halogens, 1089 Real gas(es), 232–236 Rechargeable batteries, 840, 916–917 Recrystallization, 583 Red blood cells, 607 Redheffer, Charles, 253 Redheffer’s perpetual motion machine, 253 Redox reactions See Oxidation–reduction reaction(s) Red phosphorus, 1077 Reducing agents, 179, 180, 901 Reduction, 175, 890 See also Oxidation– reduction reaction(s) Refining, 1104, 1106–1107 Reflection, angle of, 535 Refractory materials, 554 Relative abundance, of isotopes, 67 Relative concentration, 791–792, 794 Relative solubility, 812 Relative standard entropies, 860–862 Relative zero, 859–860 Reliability, of measurements, 20–26 rem (roentgen equivalent man), 966 Renewable energy, 284 Repulsive electrostatic force, among protons, 946 Resistivity, of metals, 1102, 1103 Resonance, Lewis structures and, 400, 402–404 2015/11/20 9:28 PM I-22 Index Resonance hybrids, 403 Resonance stabilization, 403 Resonance structures, 402–404, 406–407, 1000 Resting potential, 914 Retina, 454 11-cis-Retinal, 332 Retinal isomers, 454 Reversible reactions, 677, 678, 850, 851, 869 R group (side chains) of amino acids, 1039 Rhodochrosite, 1115 Rhomohedral unit cells, 537 Ribonucleic acid (RNA), 1047 Ribose, 1047 Ribosomes, 1051 Ripening agent, ethene as, 992 Ritonavir, 546 RNA (ribonucleic acid), 1047 Roasting, 1105 Rock candy, 583 Rocks, uranium/lead dating of, 954–955 Rock salt structure, 549 Rods, 454 Roentgen, 966 Roentgen equivalent man (rem), 966 Roman Pantheon, 554 Roosevelt, Franklin, 956–958 Root mean square velocity, 228–230 Rotation, of polarized light, 986–987 Rotational energy, 849, 862 Ru-92, 944 Rubbing alcohol See Isopropyl alcohol Rubidium, 63, 369 Rubies, color of, 1127–1128 Rusting, 10, 926 Rutherford, Ernest, 53–55, 57, 941, 963 Rutherfordium, 57 Rutile, 1103, 1113, 1114 Rydberg, Johannes, 309 Rydberg constant, 309, 318 Rydberg equation, 309, 318, 321 S S See Entropy(-ies) S° (standard molar entropies), 859–863 s (second), 14–15 ∆S See Entropy change Saccharin, 428 Sacramento, California, 259 Sacrificial electrode, 927 SAE scale, 501 Safe Drinking Water Act (SDWA), 521, 618 Salicylic acid, reaction between ethanoic acid and, 1011 Salmonella, irradiation of foods to kill, 969 Salt(s) acid–base properties of, 750–757 from acid–base reactions, 170 density of, 19 electrolysis of molten, 921 organic compounds vs., 123 solutions as acidic, basic, or neutral, 755–757 table See Sodium chloride Salt bridges, 896, 1045 Saltpeter, 1076 Salt water, 158–159 Sand, specific heat of, 259 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 22 San Francisco, California, 259 Sanger, Frederick, 1030 Saran, 566 Saturated fats, 1033 Saturated fatty acid, 1031 Saturated hydrocarbons See Alkanes Saturated solution, 582, 815 Scanning tunneling microscope (STM), 46 Schrödinger, Erwin, 297, 298 Schrödinger equation, 317–320, 340, 460–461 Schrödinger’s cat, 297–298 Science, Scientific approach to knowledge, 3–5 Scientific law, 3–5 Scientific notation, 17 Scientific revolution, Scintillation counter, 948 SCN- ligand, chemical analysis with, 1148 Screening (shielding), 342, 353–355 Scuba diving, 202–203, 217–218 SDWA (Safe Drinking Water Act), 521, 618 Seawater, 571–573, 816, 1091 sec-Butyl substituent, 990 Second (s) (unit), 14–15 Secondary structure, protein, 1043–1046 Secondary valence, 1132 Second ionization energy (IE2), 361, 364–365 Second law of thermodynamics, 840, 843–852 Second-order integrated rate law, 637–638, 641 Second-order reaction, 629–631, 641 Second-order reaction half-life, 640, 641 Seed crystals, 547 Seesaw geometry, 434, 436, 439 Selective oxidation, 905 Selective precipitation, 816–820 Selenium, 57 Semiconductor(s), 63, 533, 555–557 Semipermeable membrane, 603, 604 Sensors, chemical, 1127 Separation, in metallurgy, 1104 Serine, 1039, 1040 SHE half-cell, 898–900, 902 —SH groups, 181 Shielding (screening), 342, 353–355 Shroud of Turin, 954 SI (International System of Units), 13–14 Sickle-cell anemia, 1044, 1059 Sievert (Sv), 966 s*2p antibonding orbital, 466, 467 Sigma (s) bonds, 452 s2p bonding orbital, 466, 467 Significant figures, 22–25, 734 Silica, 553, 555, 1066, 1069 Silicate ceramics, 553–554 Silicate glass, 555 Silicates, 553, 1066–1069 Silicon, 63 carbon vs., 981–982 doping of, 557 electron configuration of, 347 ionization energies of, 365 Silicon carbide, 554, 1074 Silicon dioxide, 547, 548 Silicon nitride, 554 Silicon oxide, 1074 Silk, 1045 Silver, 67, 259, 276, 357 Silver brass, 1118 Silver bromide, 810 Silver chloride, 132, 161, 809, 810, 823 Silver chromate, 810 Silver iodide, 810 Silver ions, 821, 1133 Silver nitrate, 161, 393, 816 Silver plating, 919 Simple carbohydrates, 1035–1037 Simple cubic structure, 538–539, 1112 Simple cubic unit cell, 538–539 Single bond(s), 91 bond energy of, 412 bond length of, 415 covalent, 394 double bonds vs., 454, 996 Single-nucleotide polymorphisms (SNPs), 1052 Single-walled nanotubes (SWNT), 552 Sintering, 1107 SI unit(s) base units, 13–14 of density, 18 derived units, 17–18 of energy, 252 of length, 14, 18 of mass, 14, 18 prefix multipliers, 17 of pressure, 199–200 of speed, 17 of temperature, 15–16 of time, 14–15 of volume, 18 Skunk, smell of, 980 Skydiving, supersonic, 197–198 SLAC (Stanford Linear Accelerator), 963–964 Slag, 1105 Smell, sense of, 979–980 Smelting, 1105 Smithsonite, 1118 Smog, photochemical, 282 Smoke, 609 Snorkels, extra-long, 205 Snowflake, 534 SNPs (single-nucleotide polymorphisms), 1052 Soap, 444, 608–610 Socrates, 726 Soda ash, 96 Soda-lime glass, 555 Sodium, 57, 63 charge of, 97, 98 electron affinity of, 366 electron configuration of, 345, 359 electronegativity of, 398 electron sea model for, 415, 416 emission spectrum of, 310 flame tests for, 311 ionization energies of, 361, 362, 364, 365 Lewis structure of, 387 properties of, 88, 369–370 reaction between methanol and, 1005 2015/11/20 9:28 PM reaction between sulfur and, 387–388 ∆H°f for compounds containing, 276 Sodium acetate, 582, 781, 782, 815 Sodium bicarbonate (baking soda) carbon dioxide from, 1076 ions from dissociation of, 750 in medicine, 393 polyatomic ions in, 95 reaction between hydrochloric acid and, 173, 174 uses of, 726 Sodium borates, 1070 Sodium carbide, 1074 Sodium carbonate, 162, 726 Sodium chlorate, 1093 Sodium chloride acidity of solutions containing, 755 Born–Haber cycle for p roduction of, 388–391 chemical formula for, 90 conductivity of, 392–393 as crystalline solid, 545, 547 decomposition of sugar vs., 981 density of, 19 electrolysis of, 921–923 formation of, 47–48, 89, 1103 formula unit for, 94–95 as ionic compound, 96 lattice energy of, 388–392 melting of, 392–393 properties of sodium and chlorine vs., 88 reaction between potassium iodide and, 164 from redox reaction, 176 in seawater, 572–573 solute and solvent interactions in solution, 158 unit cell for, 549 in water, 497, 573, 578, 581–582, 593 Sodium chlorite, 1093 Sodium fluoride, 393, 755, 813 Sodium hydroxide in Arrhenius model, 727 pH of, 734 reaction between hydrochloric acid and, 168–169 reaction between hydrofluoric acid and, 170 reaction between propanoic acid and, 1010 reaction between water and, 578, 1005 strength of, 746 and sulfurous acid, 805–806 titration with formic acid, 800–805 titration with hydrochloric acid, 795–799 uses of, 726 Sodium hypochlorite, 95 Sodium iodide, 922 Sodium ion(s) cations vs., 59–60 electron configuration of, 359 in human nerve cells, 914 nerve signal transmission and, 337–338 solubility and, 161 Sodium methoxide, 1005 Sodium nitrite, 95, 100, 1081 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 23 Index Sodium oxide, 107 Sodium phosphate compounds, 1082 Sodium sulfide, 1087 Soft drinks, pH of, 734 Solar power, 284 Solar-powered electrolytic cell, 919 Solid(s), 485, 532–569 See also Crystalline solid(s) amorphous, 488 ceramics, cement, and glass, 553–555 entropy change associated with change in state of, 848–852 equilibria involving, 687–688 and graphene’s discovery, 533–534 intermolecular forces in, 489–502 ionic, 548–550 molecular comparison with other phases, 486–489 network covalent atomic, 550–553 on phase diagram, 517–518 polymers, 557–560 properties of, 487 relative standard entropies of, 860 semiconductors, 555–557 solubility of, temperature dependence of, 582–583 standard state for, 275, 859 sublimation and fusion of, 512–514 unit cells and basic structures of, 537–544 X-ray crystallography of, 534–536 Solid aerosols, 609 Solid emulsion, 609 Solid matter, 6, Solid solution, 573 Solubility alloys with limited, 1110–1111 of amphoteric metal hydroxides, 824–825 complex ion equilibria and, 823–824 defined, 573 effect of intermolecular forces on, 574–577 and entropy, 574 of gases in water, 583–585 molar, 809–812 relative, 812 temperature dependence of, 582–583 Solubility equilibria, 778, 809–816 common ion effect on, 812–813 molar solubility, 809–812 pH and, 814 Solubility product constant (Ksp), 809–812 molar solubility and, 809–812 and reaction quotient, 815–816 relative solubility and, 812 Solubility rules, 161, 809 Soluble compounds, 160–162, 815 Solute(s), 151, 572 interactions between, 158, 574, 575 interactions with solvents, 597 intermolecular forces acting on, 574–577, 597 van’t Hoff factors for, 605–606 Solution(s), 570–621 See also Acid–base chemistry; Aqueous solution(s) boiling point elevation, 600–602 colligative properties of, 593–608 I-23 colloids, 608–610 concentrated, 151, 585, 594–595, 734 concentration of, 151–154, 585–592 defined, 151, 572 dilute, 151, 585 dilution of, 154–156 electrolyte, 158–160 energetics of formation, 577–581 entropy and, 574, 594–595 equilibrium processes in, 581–585 freezing point depression, 600–603 gaseous, 573 hyperosmotic, 607, 618 hyposmotic, 607 ideal, 597 intermolecular forces in, 574–577 intravenous, 608 isosmotic (isotonic), 607–608 liquid, 573 molarity of, 151–154 neutral, 733, 734 nonelectrolyte, 159, 160 nonideal, 597–599 saturated, 582, 815 separation using, 1104 solid, 573 standard state for substances in, 859 stock, 154–155 supersaturated, 582, 815 thirsty, 571–573, 594–595 transition metal ions in See Complex ion equilibria unsaturated, 582, 815 vapor pressure of, 597–599 Solution stoichiometry, 156–157 Solvent(s), 151, 572 interactions between, 574, 575, 597 interactions of solutes and, 158, 574, 575 intermolecular forces acting on, 574–577, 597 nonpolar, 576 polar, 576 Soot, 1073 s orbitals, 319, 323–326 1s, 323–324, 328 2s, 325–326, 342–343 3s, 325–326 Sorosilicates (pyrosilicates), 1067, 1069 Sound, speed of, 299 sp2 hybridization, 450–454, 458 sp3d2 hybridization, 457, 458 sp3d hybridization, 456–457, 458 sp3 hybridization, 448–450, 458 Space-filling molecular models, 92, 93, 109 Specific heat capacity (Cs), 259, 521 Spectator ions, 166, 167 Spectra, 309–311 Spectrochemical series, 1145 Spectrometers, 628 Spectroscopy, 628 Speed, SI unit for, 17 Sphalerite, 1103, 1118 sp hybridization, 454–456, 458 Sphygmomanometer, 201 Spin-pairing, 446–447 Spin quantum number (ms), 318, 319, 340–341 2015/11/20 9:28 PM I-24 Index Spin up and spin down, 340 Spontaneity change in Gibbs free energy as criterion for, 856 conditions for, 875 effect of ∆S, ∆H, and temperature on, 856–859 in oxidation–reduction reactions, 893–897, 902–905, 907 Spontaneous process(es), 841–843 decrease in Gibbs free energy and, 856 endothermic, 843–844 exothermic, 852 making nonspontaneous processes into, 867 mixing, 572–574 in voltaic (or galvanic) cells, 893–897 Square planar complexes, 1139–1140, 1147 Square planar geometry of complex ions, 1135 molecular, 435, 436, 438, 439 Square pyramidal geometry, 435, 436 S°rxn (entropy change for a reaction), 859–865 Stability, valley of, 946–948 Stainless steels, 1114, 1115 Stalactites, 814 Stalagmites, 814 Standard atomic weight, 65–69, 107 Standard cell potential (E°cell), 896, 906–909 Standard change in free energy (∆G°rxn), 863–876 calculating, 863–870 and change in free energy, 909 and equilibrium constant, 873–876 from free energies of formation, 865–866 and “free energy” concept, 868–869 with nonstandard conditions, 870–873 and standard cell potential, 906–907, 909 from standard enthalpies of formation, 864–865 for stepwise reaction, 867–868 Standard electrode potentials, 898–905 and direction of redox reaction, 902–905 and solubility of metals in acids, 905 standard cell potential from, 898–902 Standard emf See Standard cell potential (E°cell) Standard enthalpy change (∆H°), 275–280 Standard enthalpy of formation (∆H°f), 275–280 Standard enthalpy of reaction (∆H rxn ° ), 277–278, 864–865 Standard entropy change for a reaction (S°rxn), 859–865 Standard free energies of f ormation, 865–866 Standard heat of formation See Standard enthalpy of formation (∆H°f) Standard hydrogen electrode (SHE) half-cell, 898–900, 902 Standard molar entropies (S°), 859–863 Standard state, 275–276, 859, 870 Standard temperature and pressure (STP), molar volume at, 211–212 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 24 Stanford Linear Accelerator (SLAC), 963–964 Starch, 1037, 1038 Stars, neutron, 55, 82 State function, 253–255, 845 States of matter, 5–7 changing between, 488–489 See also Phase transition(s) critical point for, 511–512 differences between, 486–488 entropy change associated with change in, 848–852 Stationary states, 310, 311 Steady state, 952 Steam burn, 504 Stearic acid, 1031–1033 Steel galvanizing, 1118 production of, 1082, 1084, 1116 stainless, 1114, 1115 Steel alloys, 1114–1116 Stepwise reactions, standard change in free energy for, 867–868 Stereoisomerism, 1139–1142 geometric, 996–997, 1137–1140 optical, 985–987, 1036, 1140–1142 Stereoisomers, 985, 1137 Stern–Gerlach experiment, 357 Steroids, 1034 STM (scanning tunneling m icroscope), 46 Stock solutions, 154–155 Stoichiometry, 141–145 defined, 139, 141 of electrolysis, 924–925 involving enthalpy change, 269–270 molar volume and, 222–223 for pH changes in buffer s olutions, 786 reaction, 141–145, 221–223, 269–270 solution, 156–157 Storage proteins, 1038 STP (standard temperature and pressure), molar volume at, 211–212 Strassmann, Fritz, 956 Strong acid(s), 160, 729 hydronium ion sources in, 737 pH of, mixed with weak acid, 743–744 titration with strong base, 795–799 titration with weak base, 805 Strong base(s), 746, 748 cations as counterions of, 754 hydroxide ion concentration and pH of, 748–749 titration of diprotic acid with, 805–806 titration with strong acid, 795–799 titration with weak acid, 800–805 Strong electrolytes, 159, 160, 605–608, 729 Strong-field complexes, 1143 Strong-field ligands, 1145 Strong force, 946–947 Strontium, 62, 63 Strontium hydroxide, 746 Structural formulas, 91, 983–985 Structural isomers, 983–985, 1035–1036, 1137–1139 Structural proteins, 1038 Structure of Scientific Revolutions, The (Kuhn), Styrene, 1001 Subatomic particles, 55–60 See also Electron(s); Neutron(s); Proton(s) Sublevels (subshells), 319, 341–343 Sublimation, 11, 512–514, 630 Sublimation curve, 517–519 Substance(s), 7–9 Substituents, 989–990 Substitutional alloys, 1108–1110 Substitution reactions, 997–998, 1002, 1005 Substrate, 656–657 Successive approximations, method of, 700–702 Sucrase, 657 Sucrose and artificial sweeteners, 427–428 catalytic breakup of, 657 dehydration of, 1088 density of, 19 glycosidic linkage in, 1037 hydrolysis of, 624, 627–628 Sugar(s), 123 decomposition of salt vs., 981 density of, 19 dissolution of, 11 in nucleic acids, 1047 solubility of, 582 and water, 158–160 Sulfate, 100 Sulfide(s), 98, 173, 814, 819–820, 1103 See also specific compounds Sulfites, 100, 173 Sulfonic acid groups, 181 Sulfur, 57 elemental, 1085–1086 hydrogen and metal sulfides, 1087–1088 ionization energies of, 365 Lewis structure of, 387 as molecular element, 94 on periodic table, 62 reaction with sodium, 387–388 uses of, 1085–1089 ∆H °f for compounds containing, 276 Sulfur dioxide, 767, 1086, 1088 Sulfur fluoride, 434 Sulfur hexafluoride, 410, 431, 457 Sulfuric acid, 133 acid–base reactions involving, 168 in acid rain, 765–766 expanded octets of, 410–411 formula of, 169 ionization constants for, 758 reaction between lithium sulfide and, 173 reaction between potassium hydroxide and, 170 strength of, 729 structure of, 725 uses of, 724, 1088–1089 Sulfurous acid, 105, 730, 757–758, 805–806 Sulfur oxides, 282, 765–767 Sun, 284, 962–963 Supercritical fluid, 512 Supernova, 60 Superoxide, 1084 Supersaturated solution, 582, 815 Supersonic skydiving, 197–198 Surface tension, 499–500 Surfactants, 1081 2015/11/20 9:28 PM Surroundings See also Thermochemistry energy exchange of systems and, 264–265 energy flow in, 251, 252, 255, 256 entropy change in, 852–855 Suspensions, 750 Sv (Sievert), 966 Sweating, 504 SWNT (single-walled nanotubes), 552 Sylvite See Potassium chloride Synthetic elements, 964 System(s) See also Thermochemistry energy exchange of surroundings and, 264–265 energy flow in, 251, 252, 255, 256 state of, 255 Systematic error, 26 Systematic names, 97 Systolic blood pressure, 200 T T1r3 protein, 428 Table salt See Sodium chloride Talc, 1068 Tantalite, 1103 Tantalum, 1103 Tartaric acid, 133 Tastant, 428 Taste, of food, 428 Tc (critical temperature), 512 Technetium-99, 944 Technetium-99m, 967, 968 Tectosilicates, 1069 Tellurium, 336 Telomers, 1060 Temperature(s) absolute zero, 205 boiling point and, 507–508 critical, 512 defined, 258 entropy change and, 850, 853 equilibrium constant and, 688, 875–876 gas solubility in water and, 583 global, 140 heat capacity and, 258–260 heat vs., 258 intermolecular forces and, 490 and ion product constant for water, 733 kinetic energy and, 224, 227–228 Le Châtelier’s principle on change in, 708–710 molecular velocities and, 227–230 phase changes and, 488 pressure and, 209 reaction rate and, 642–648 scale conversions, 16 SI unit of, 15–16 solubility of solids and, 582–583 spontaneity and, 856–859 standard change in free energy from, 864–865 STP, 211–212 and thermal energy, 250 vapor pressure and, 219, 507–508, 511 viscosity and, 501 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 25 Index volume and, 204–207 water’s moderating effect on, 521 Tempering, of chocolate, 546–547 Temporary dipole (instantaneous dipole), 490 10W-40 oil, 501 Tera prefix, 17 Terminal atoms, 400 Termolecular steps, 649, 650 tert-Butyl substituent, 990 Tertiary structure, protein, 1043, 1045, 1046 Testosterone, 1034 Tetracene, 1002 Tetragonal unit cells, 537 Tetrahedral complex(es), 1142, 1147 Tetrahedral geometry, 92 of complex ions, 1135 electron, 432–433, 436, 458 molecular, 429–431, 433, 436, 439, 448, 449 Tetrahedral hole, 549, 1112 Tetrahedrons, 430, 434, 553, 1066 Tetrapeptide, 1041 Tetraphosphorus decaoxide, 1082 Tetraphosphorus hexaoxide, 1082 Thallium-201, 968 Theoretical yield, 145–151 Theories, laws vs., 4–5 Therapeutic agents, 1150 Therapeutic techniques, radioactivity in, 967 Thermal conductivity, of metals, 1103 Thermal energy, 12, 486, 623 See also Heat(s) defined, 250 dispersal of, 574 distribution of, 644 in exothermic reactions, 269 and temperature, 250 transfer of, 261–262 vaporization and, 502–503 Thermal equilibrium, 258 Thermal shock, 554 Thermite reaction, 279 Thermochemical equations, 269–270 Thermochemistry, 248–295 See also Energy(-ies) of chemical hand warmers, 249–250 enthalpy, 267–270 enthalpy change for chemical reactions, 270–280 environmental impacts of energy use, 280–284 first law of thermodynamics, 253–258 internal energy change for chemical reactions, 264–266 and nature of energy, 250–252 pressure–volume work, 262–264 quantifying heat, 258–262 Thermodynamics, 838–887 See also Equilibrium(–a) chemical reactions, 859–869 defined, 253 entropy in, 844–855, 859–863 and equilibrium constant, 873–876 first law of, 253–258, 840 free energy change of reaction under nonstandard conditions, 870–873 I-25 Gibbs free energy, 855–859 heat transfer, 852–855 nature’s heat tax and, 839–841 reaction rate and, 842, 843 of reversible reaction, 869 second law of, 840, 843–852 of spontaneous vs nonspontaneous processes, 841–843 standard change in free energy, 863–876 state changes, 848–852 third law of, 859–863 Thermoluminescent dosimeters, 948 Thiocyanate ion, 1133 Thiocyanato ligand, 1139 Thiol groups, 181 Third ionization energy (IE3), 361 Third law of thermodynamics, 859–863 Thirsty solutions, 571–573, 594–595 Thomson, J J., 51–53 Thorium-232, decay of, 948 Threonine, 1040 Threshold frequency, 306, 307 Thymine, 498, 499, 1047, 1048 Thymol blue, 809 Thymolphthalein, 809 Thyroid gland, radiotracer used for, 967 Time concentration and, 634–641 product/reactant concentrations as function of, 625–626 SI unit of, 14–15 Tin, 57, 99, 1117 Titanium, 19, 1113–1114 Titanium oxide, 1114 Titration, 171, 628 See also Acid–base titration Titration curves, 795–806 Tokamak fusion reactor, 963 Toluene, 545–546, 576, 1001 Torr, 199 Torricelli, Evangelista, 199 Total force, of a gas, 227 Total intensity, normalization of, 67 Total pressure, 210, 216–217 Toxaphene, 590 Toyota Mirai (fuel-cell vehicle), 284, 890 Trajectory, 315–316 Trans–cis isomers See Geometric isomerism Transition(s) See also Phase transition(s) in Bohr model, 310, 311 in hydrogen atom, 320–323 quantum-mechanical orbital, 320 Transition metal(s), 63, 98, 350, 1126–1157 atomic radii and, 355–356 and colors of rubies and emeralds, 1127–1128 coordination compounds, 1132–1150 crystal structures for, 1108 functions in human body, 1148 inner, 347–348, 350–351 ion formation by, 64 properties of, 1128 –1131 sources, products, and properties of, 1113–1118 valence electrons for, 347–348 Transition metal ions, 357–358 See also Complex ion equilibria 2015/11/20 9:28 PM I-26 Index Transition state (activated complex), 643 Translational energy, 849, 862 Transmutation, nuclear, 963–964 Transport proteins, 1038 Transuranium elements, 964 Tremolite, 1068 Triads, 338 1,1,2-Trichloro-1,2,2-trifluoroethane, 634 Trichlorofluoromethane, 634 Triclinic unit cells, 537 Triglycerides, 1032–1033 Trigonal bipyramidal geometry, 1092 electron, 434–436, 458 molecular, 431, 436, 439, 456–457 Trigonal planar geometry electron, 436, 458 molecular, 429, 430, 436, 439, 450 Trigonal pyramidal geometry, 432–433, 436, 438, 439, 443 Trihalides, 1070–1071 Trimethylamine, 1012 Triolein, 1033 Tripeptide, 1041 Triple bond(s), 395 bond energy of, 412 bond length of, 415 carbon’s ability to form, 980, 981 covalent, 395 sp hybridization and, 454–456 in structural formulas, 984 Triple point, 517–519 Triprotic acids, 730, 757–758 Tristearin, 1032–1033 Trona, 96 Tryptophan, 1040 T-shaped geometry, 434, 436 Tums, 750 Tungsten carbide, 1075 Turquoise, 1128 Two-phase region, 1110–1111 Tyndall effect, 610 Tyrosine, 1040 U Ulcers, 736 Ultraviolet (UV) radiation, 302, 416 Uncertainty principle, 314–315 Unimolecular elementary step, 649, 650 Unit cells, 537–544 for closest-packed structures, 543–544 cubic, 537–542 for ionic solids, 548–550 Unit conversion problems, 26–30 United States, energy consumption in, 280–281, 765 U.S Department of Agriculture (USDA), 969 U.S Department of Energy (DOE), 142, 280, 1052 U.S Environmental Protection Agency (EPA), 114, 282, 521, 590 U.S Food and Drug Administration (FDA), 114, 969, 1033 Units of measurement, 13–20 See also SI unit(s) Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 26 Universe age of, 955 entropy of, 852, 855 Unsaturated fat, 1033 Unsaturated fatty acids, 1032 Unsaturated hydrocarbons, 992–997 See also Alkenes; Alkynes Unsaturated solutions, 582, 815 Unsaturation, effect of, 1032 Uracil, 1047 Uranic rays, 940 Uranium, 56, 1103 Uranium-235, 79, 956–960 Uranium-238, 670, 942, 948, 956 Uranium fuel rods, 959 Uranium/lead dating, 954–955 Urea, 188, 981 USDA (U.S Department of Agriculture), 969 UV (ultraviolet) radiation, 302, 416 V V (volt), 895 c See Frequency Valence, 1132 Valence bands, 556, 557 Valence bond theory, 383, 445–460 bonding in coordination compounds and, 1142–1143 double bonds in, 450–454 hybridization of atomic o rbitals, 447–460 Lewis model and, 452 Lewis theory and, 458 orbital overlap in, 445–447 Valence electrons, 345, 347–351, 386–387 Valence shell electron pair repulsion (VSEPR) theory, 427–444, 1092– 1093 bent geometry, 433, 436, 439, 443 linear geometry, 429, 430, 435, 439, 443 lone pairs effect, 432–437 molecular shape and polarity, 440–444 octahedral geometry, 431, 435, 436, 439, 457 predicting molecular geometries with, 437–440 seesaw geometry, 434, 436, 439 square planar geometry, 435, 436, 438, 439 square pyramidal geometry, 435, 436 summary of, 435 tetrahedral geometry, 429–433, 436, 439, 443, 448, 449 trigonal bipyramidal geometry, 431, 434–436, 439, 456–457 trigonal planar geometry, 429, 430, 436, 439, 443, 450 trigonal pyramidal geometry, 432–433, 436, 438, 439, 443 T-shaped geometry, 434, 436 Valine, 1040 Valley of stability, 946–948 Vanadinite, 1103 Vanadium, 357, 1101–1103, 1109–1110 Vanadium ions, 357 Vandate compounds, 1102 Van der Waals, Johannes, 233 Van der Waals constants, 233 Van der Waals equation, 235 Van der Waals radius, 352 Vanillin, 1007 Van’t Hoff factor (i), 605–606 Vaporization, 502–512 Clausius–Clapeyron equation and, 508–511 critical point, 511–512 energetics of, 503–505 heat of, 504–505, 510, 514 process of, 502–503 vapor pressure and dynamic equilibrium, 505–511 Vaporization curve, 517–519 Vapor pressure, 219 defined, 506 and dynamic equilibrium, 505–511, 593–594 of solutions, 597–599 and strong electrolytes, 606–607 temperature and, 219, 508–509, 511 Vapor pressure lowering (∆P), 593–596 Variational method, 461 Vector addition, 442 Vector quantities, 441 Vegetarian diet, nature’s heat tax and, 840 Velocity(-ies) in classical mechanics, 315–316 of electron, 315 molecular, 227–230 and position as complementary property, 317 root mean square, 228–230 Venus (planet), 140 Venus of Dolni, 553 Vibrational energy, 862 Vinegar, 725 Viscosity, 501 Visible light, 300–302 Vision, 454 Vital force, 981 Vitalism, 981 Vitamins, 479 Vitreous silica, 555 Volatility, 8, 503, 597–599 Volt (V), 895 Voltaic (galvanic) cells, 893–897 anode, cathode, and salt bridge in, 896 batteries as, 914–918 concentration cells, 912–914 current and potential difference in, 895–896 electrochemical cell notation, 897 electrolytic cells vs., 920–921 Volume constant-volume calorimetry, 264–266, 272 gas amount and, 207–208 Le Châtelier’s principle on change in, 706–707 molar, 211–212, 222–223, 232–233 parts by, 588–589 percent mass to, 608 pressure and, 202–204 2015/11/20 9:28 PM pressure–volume work, 262–264 of real gas particles, 233 SI unit for, 18 stoichiometry and, 222–223 temperature and, 204–207 unit cell, 540–541 VSEPR theory See Valence shell electron pair repulsion theory W Warren, J Robin, 736 Washing soda, 1075–1076 Water, 2, amphotericity of, 732 Arrhenius definition of acids and bases and, 727 autoionization of, 732–734 boiling point of, 504, 508 charge distribution in, 158 chemical formula for, 90–91 collecting gases over, 219–221 decomposition of, 48, 284 density of, 19 electrolysis of, 919, 1083–1084 empirical formula for, 114–115 entropy of surroundings and freezing of, 852, 853 ethanol mixed with, 575 from fossil fuel combustion, 281 free energy change for, 870–872 freezing point depression/boiling point elevation constants for, 601 geometry of, 433, 441 gravity and behavior of, 485–486 hard, 162, 811 heat capacity of, 259, 260 heating curve for, 514–517 heat of fusion for, 513–514 heat of vaporization of, 504 hexane mixed with, 575–576 hydrogen bonding in, 496, 520 Lewis structure of, 394–395 as ligand, 1133 on Mars, 520, 521 meniscus of, 502 obtaining hydrogen from, 867 phase diagram for, 517–519 polarity of, 441, 444, 494, 576 properties of, 87–89, 520–521 reaction between calcium and, 890 reaction between carbon dioxide and, 765, 766 real gas behavior of, 235 in seawater, 572–573 sodium chloride in, 497, 573, 578, 581–582, 593 solubility in, 577, 583–585 specific heat of, 259 spherical droplets of, 500 states of, 486 and sugar, 158–160 thermal energy distributions for, 502–503 Z07_TRO5187_04_SE_INDX_I-1-I-28v2.0.1.indd 27 I-27 Index van der Waals constants for, 233 viscosity of, 501 Water atomization, 1107 Water pollution, 521 Waters of hydration, 101 Water softeners, 618 Water vapor, condensation of, 504 Watson, James D., 499, 535, 1028, 1029, 1050 Watt (W), 252 Wave function (c), 317 Wavelength (l), 300 de Broglie, 313–314 energy and, 307 frequency and, 301, 307 Wave nature of electrons, 311–317 of light, 299–301 of matter, 311–317 Wave–particle duality of light, 298, 308 Weak acid(s), 160 acid ionization constants for, 730–732, 737–738 in buffer solution, 780–781 cations as, 754–755 diprotic, 760–761 hydronium ion sources in, 737–741, 743 percent ionization of, 742–743 pH of mixtures containing, 743–745 titration with strong base, 800–805 Weak base(s), 746–748 anions as, 751–754 in buffer solution, 780–781 hydroxide ion concentration and pH of, 748–749 titration with strong acid, 805 Weak electrolytes, 160, 729 Weak-field complexes, 1143 Weak-field ligands, 1145 Weather, 198–199 Weighing, 21, 107–108 Weight, 14 atomic, 65–69, 107 molecular, 107 Weighted linear sum, of molecular orbitals, 461–463 Werner, Alfred, 1126, 1132, 1135 Western bristlecone pine trees, 953 Wet chemistry, 818 Wetting agent, 1104 Whipped cream, 609 White light spectrum, 300, 301, 308–309 White phosphorus, 1077, 1081–1082 Wilhelmy, Ludwig, 624, 627–628 Wilkins, Maurice, 535 Willemite, 1067 Window glass, 555 Wind power, 284 Wines, pH of, 734 Winkler, Clemens, 61 Witt, Otto N., 778, 779 Wöhler, Friedrich, 978, 981 Wood alcohol See Methanol Wood frogs (Rana sylvatica), 603 Work defined, 12, 250 in first law of thermodynamics, 256–258 internal energy change and, 256–258 pressure–volume, 262–264 X Xenon as atomic solid, 547 as crystalline solid, 545 nonideal behavior of, 234 on periodic table, 63 properties of, 372 reaction between fluorine and, 372 van der Waals constants for, 233 Xenon difluoride, 435 x is small approximation, 700, 702, 738–740, 761, 783–785 X-ray crystallography, 383, 534–536 X-ray diffraction, 534–536 X-rays, 301, 302, 303, 940 Y Yield of reactions actual, 146 percent, 146–148 theoretical, 145–151 Yucca Mountain, Nevada, 959 Z Z See Atomic number Zeff (effective nuclear charge), 342, 352–356 Zeolites, 1076 Zero entropy, 860 Zero-order integrated rate law, 638, 641 Zero-order reaction, 629–631, 641 Zero-order reaction half-life, 640, 641 Zinc alloy of copper and, 1118 crystal structure of, 548 in dry-cell batteries, 914–915 electrochemical cell of copper ions and, 910 in galvanized nails, 927 in human body, 1148 reaction between copper ions and, 893–897 reaction between hydrochloric acid and, 103, 905 sources, properties, and products of, 1118 Zinc blende structure, 549, 551 Zinc ions, 358 Zinc oxide, 393, 1105 Zinc phosphate, 1118 Zinc silicate (calamine), 1118 Zinc sulfide, 549, 551, 1087 Zwitterion, 1041 2015/11/20 9:28 PM This page intentionally left blank Main groups 1Aa 1 H 1.008 2A Li Be 6.94 9.012 11 Na 12 Mg 22.99 24.31 19 K Main groups Metals Metalloids Transition metals 26 Fe 8B 27 Co 54.94 55.85 58.93 43 Tc 44 Ru 45 Rh [98] 101.07 102.91 20 Ca 3B 21 Sc 4B 22 Ti 5B 23 V 6B 24 Cr 7B 25 Mn 39.10 40.08 44.96 47.87 50.94 52.00 37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 85.47 87.62 88.91 92.91 95.96 56 Ba 57 La 91.22 55 Cs 132.91 137.33 138.91 178.49 180.95 183.84 186.21 190.23 87 Fr 88 Ra 89 Ac 104 Rf 105 Db 106 Sg 107 Bh [223.02] [226.03] [227.03] [261.11] [262.11] [266.12] 58 Ce 140.12 72 Hf Lanthanide series Actinide series 73 Ta 5A 15 N 6A 16 7A 17 4.003 B 4A 14 C O F 10 Ne 10.81 12.01 14.01 16.00 19.00 20.18 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar 26.98 28.09 30.97 32.06 35.45 39.95 3A 13 Nonmetals 8A 18 He 10 28 Ni 1B 11 29 Cu 2B 12 30 Zn 58.69 63.55 65.38 69.72 72.63 74.92 78.96 79.90 83.80 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29 78 Pt 79 Au 80 Hg 81 Tl 82 Pb 83 Bi 84 Po 85 At 86 Rn 192.22 195.08 196.97 200.59 204.38 207.2 208.98 [208.98] [209.99] [222.02] 108 Hs 109 Mt 110 Ds 111 Rg 112 Cn 114 Fl [269.13] [268.14] [271] [272] [285] 115 * 116 Lv [264.12] 113 * 117 * 118 * 59 Pr 60 Nd 61 Pm 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 69 Tm 70 Yb 71 Lu 140.91 144.24 [145] 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr [247.07] [247.07] [251.08] [252.08] [257.10] [258.10] [259.10] [262.11] 74 W 75 Re 76 Os 77 Ir 46 Pd 90 Th 91 Pa 92 U 93 Np 94 Pu 95 Am 232.04 231.04 238.03 [237.05] [244.06] [243.06] 47 Ag 48 Cd 31 Ga 32 Ge 49 In 50 Sn [289] a The labels on top (1A, 2A, etc.) are common American usage The labels below these (1, 2, etc.) are those recommended by the International Union of Pure and Applied Chemistry Atomic masses in brackets are the masses of the longest-lived or most important isotope of radioactive elements *The names of elements 113, 115, 117, and 118 are currently under review by IUPAC 33 As 51 Sb 34 Se 52 Te [292] 35 Br 53 I 36 Kr 54 Xe List of Elements with Their Symbols and Atomic Masses Element Actinium Aluminum Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Bohrium Boron Bromine Cadmium Calcium Californium Carbon Cerium Cesium Chlorine Chromium Cobalt Copernicium Copper Curium Darmstadtium Dubnium Dysprosium Einsteinium Erbium Europium Fermium Flerovium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Hassium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Livermorium Lutetium Magnesium Manganese Symbol Atomic Number Atomic Mass Element Ac Al Am Sb Ar As At Ba Bk Be Bi Bh B Br Cd Ca Cf C Ce Cs Cl Cr Co Cn Cu Cm Ds Db Dy Es Er Eu Fm Fl F Fr Gd Ga Ge Au Hf Hs He Ho H In I Ir Fe Kr La Lr Pb Li Lv Lu Mg Mn 89 13 95 51 18 33 85 56 97 83 107 35 48 20 98 58 55 17 24 27 112 29 96 110 105 66 99 68 63 100 114 87 64 31 32 79 72 108 67 49 53 77 26 36 57 103 82 116 71 12 25 227.03a 26.98 243.06a 121.76 39.95 74.92 209.99a 137.33 247.07a 9.012 208.98 264.12a 10.81 79.90 112.41 40.08 251.08a 12.01 140.12 132.91 35.45 52.00 58.93 285a 63.55 247.07a 271a 262.11a 162.50 252.08a 167.26 151.96 257.10a 289a 19.00 223.02a 157.25 69.72 72.63 196.97 178.49 269.13a 4.003 164.93 1.008 114.82 126.90 192.22 55.85 83.80 138.91 262.11a 207.2 6.94 292a 174.97 24.31 54.94 Meitnerium Mendelevium Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium Potassium Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Roentgenium Rubidium Ruthenium Rutherfordium Samarium Scandium Seaborgium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium *b *b Symbol Atomic Number Atomic Mass Mt Md Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rg Rb Ru Rf Sm Sc Sg Se Si Ag Na Sr S Ta Tc Te Tb Tl Th Tm Sn Ti W U V Xe Yb Y Zn Zr 109 101 80 42 60 10 93 28 41 102 76 46 15 78 94 84 19 59 61 91 88 86 75 45 111 37 44 104 62 21 106 34 14 47 11 38 16 73 43 52 65 81 90 69 50 22 74 92 23 54 70 39 30 40 113 115 268.14a 258.10a 200.59 95.96 144.24 20.18 237.05a 58.69 92.91 14.01 259.10a 190.23 16.00 106.42 30.97 195.08 244.06a 208.98a 39.10 140.91 145a 231.04 226.03a 222.02a 186.21 102.91 272a 85.47 101.07 261.11a 150.36 44.96 266.12a 78.96 28.09 107.87 22.99 87.62 32.06 180.95 98a 127.60 158.93 204.38 232.04 168.93 118.71 47.87 183.84 238.03 50.94 131.293 173.05 88.91 65.38 91.22 284a 288a a Mass of longest-lived or most important isotope The names of these elements have not yet been decided b Z08_TRO5187_04_SE_ENP_002-005v2.0.2.indd 2015/11/20 9:01 PM Conversion Factors and Relationships Length SI unit: meter (m) m = 1.0936 yd cm = 0.39370 in in = 2.54 cm (exactly) km = 0.62137 mi mi = 5280 ft = 1.6093 km ∘ A = 10 -10 m Temperature SI unit: kelvin (K) K = -273.15 °C Energy (derived) SI unit: joule (J) J = kg # m2 >s2 = -459.67 °F = 0.23901 cal = 1C#V K = °C + 273.15 = 9.4781 * 10 -4 Btu (°F - 32) °C = 1.8 °F = 1.8 (°C) + 32 Volume (derived) SI unit: cubic meter (m3) L = 10 -3 m3 = dm3 = 103 cm3 = 1.0567 qt gal = qt = 3.7854 L cm3 = mL in3 = 16.39 cm3 qt = 32 fluid oz Pressure (derived) SI unit: pascal (Pa) Pa = N>m2 = kg>(m # s2) atm = 101,325 Pa = 760 torr = 14.70 lb>in2 bar = 105 Pa torr = mmHg cal = 4.184 J eV = 1.6022 * 10 -19 J Mass SI unit: kilogram (kg) kg = 2.2046 lb lb = 453.59 g = 16 oz amu = 1.66053873 * 10 -27 kg ton = 2000 lb = 907.185 kg metric ton = 1000 kg = 2204.6 lb Geometric Relationships p = 3.14159 c Circumference of a circle = 2pr Area of a circle = pr Surface area of a sphere = 4pr pr Volume of a cylinder = pr 2h Volume of a sphere = Fundamental Constants Atomic mass unit amu 1g = 1.66053873 * 10 -27 kg = 6.02214199 * 1023 amu Avogadro’s number NA Bohr radius a0 = 6.02214179 * 1023 >mol Boltzmann’s constant k = 1.38065052 * 10 -23 J>K Electron charge e = 1.60217653 * 10 -19 C Faraday’s constant F = 9.64853383 * 104 C>mol Gas constant R Mass of an electron me = 5.48579909 * 10 -4 amu = 9.10938262 * 10 -31 kg Mass of a neutron mn = 1.00866492 amu = 1.67492728 * 10 -27 kg Mass of a proton mp = 1.00727647 amu = 1.67262171 * 10 -27 kg Planck’s constant h = 6.62606931 * 10 -34 J # s Speed of light in vacuum c = 2.99792458 * 108 m>s (exactly) = 5.29177211 * 10 -11 m = 0.08205821 (L # atm>(mol # K) = 8.31447215 J>(mol # K) SI Unit Prefixes a f p n m m c d k M G T P E atto femto pico nano micro milli centi deci kilo mega giga tera peta exa 10-18 10-15 10-12 10-9 10-6 10-3 10-2 10-1 103 106 109 1012 1015 1018 Z08_TRO5187_04_SE_ENP_002-005v2.0.2.indd 2015/11/20 9:01 PM Selected Key Equations Density (1.6) m d = V De Broglie Relation (7.4) Arrhenius Equation (14.5) h l = mn k = A e RT -Ea Solution Dilution (4.4) M1V1 = M2V2 Heisenberg’s Uncertainty Principle (7.4) Ideal Gas Law (5.4) PV = nRT h ∆x * m ∆v Ú 4p Dalton’s Law (5.6) Ptotal = Pa + Pb + Pc + c Energy of Hydrogen Atom Levels (7.5) Mole Fraction (5.6) na xa = ntotal En = - 2.18 * 10 -18 J a Average Kinetic Energy (5.8) KEavg = RT Root Mean Square Velocity (5.8) RT urms = A M Effusion (5.9) MB rate A = rate B A MA Van der Waals Equation (5.10) n c P + a a b d * [V - nb] = nRT V Kinetic Energy (6.2) KE = mv 2 Internal Energy (6.3) ∆E = q + w Heat Capacity (6.4) q = m * Cs * ∆T Pressure-Volume Work (6.4) w = -P ∆V Change in Enthalpy (6.6) ∆H = ∆E + P ∆V Standard Enthalpy of Reaction (6.9) ∆H rxn ° = a n p ∆H f° (products) - a nr ∆H f° (reactants) Frequency and Wavelength (7.2) c n = l Energy of a Photon (7.2) E = hn E = hc l Z08_TRO5187_04_SE_ENP_002-005v2.0.2.indd R -Ea a b + ln A T k = pz e RT n2 Coulomb’s Law (8.3) E = Ea ln k = - (collision theory) Kc and Kp (15.4) Kp = Kc(RT )∆n b (n = 1, 2, c) q1 q2 peo r pH Scale (16.5) pH = -log[H3O + ] Henderson–Hasselbalch Equation (17.2) Dipole Moment (9.6) m = qr pH = pKa + log Clausius–Clapeyron Equation (11.5) Entropy (18.3) ln Pvap = - ∆Hvap RT (linearized form) [base] [acid] S = k ln W + ln b Change in the Entropy of the Surroundings (18.5) - ∆Hvap P2 ln = c d P1 R T2 T1 ∆Ssurr = Henry’s Law (13.4) - ∆Hsys T Sgas = kH Pgas Change in Gibbs Free Energy (18.6) Raoult’s Law (13.6) Psolution = xsolvent P solvent ° ∆G = ∆H - T ∆S Freezing Point Depression (13.6) ∆Tf = m * Kf ∆G°rxn = -RT ln K Temperature Dependence of the Equilibrium Constant (18.10) Osmotic Pressure (13.6) w = MRT The Rate Law (14.3) Rate = k[A]n (single reactant) (multiple reactants) Integrated Rate Laws and Half-Life (14.4) Order Integrated Rate Law [A]t = - kt + [A]0 ∆Grxn = ∆G°rxn + RT ln Q 𝚫 G°rxn and K (18.10) Boiling Point Elevation Constant (13.6) ∆Tb = m * Kb Rate = k[A]m[B]n The Change in Free Energy: Nonstandard Conditions (18.9) t1>2 = ln[A]t = - kt + ln[A]0 t1>2 1 = kt + [A]t [A]0 ∆H r°xn ∆S°rxn a b + R T R 𝚫 G° and E°cell (19.5) ∆G° = -nF E°cell E°cell and K (19.5) Half-Life Expression In K = - [A]0 2k 0.693 = k t1>2 = k[A]0 E°cell = 0.0592 V log K n Nernst Equation (19.6) Ecell = E°cell - 0.0592 V log Q n Einstein’s Energy-Mass Equation (20.8) E = mc 2015/11/20 9:02 PM ... With each wag, the reactant approaches the activation barrier: Energy Each wag is an approach to the activation barrier Activation barrier (Ea) Reaction progress However, approaching the activation... reactants) t1 >2 = k = Ae-Ea>RT Ea ln k = a b + ln A R T k [A] 0 Elementary Step Molecularity Rate Law A ¡ products rate = k [A] A + A ¡ products rate = k [A] 2 A + B ¡ products rate = k [A] [B] A + A. .. activation barrier for the reaction b What is the value of the rate constant at 425 K? 70 A reaction has a rate constant of 0.000 122 >s at 27 °C and 0 .22 8>s at 77 °C a Determine the activation barrier