534 CHAPTER 19 Propetties of Solutions Aco FIGURE How does the orientation of HO molecules around Na" differ from that around Ci? (Crystal of NaCl in water Solent solute iniracions between water molecules and NaClalow said to dssobe Hydrated CI fon Hydrated Na ion ‘A Figure 13.3 Dissolution ofthe lone slid NaCl in water. ‘We can imagine the solution process as having three components, each with an associated enthalpy change: A cluster of n solute particles must separate from one another (AH,qq.), a cluster of m solvent particles separate from one another (AHfjen) and these solute and solvent particles mix (AHpyx)- 1, (solute), =n solute Hecate 2. (solvent), = msolvent AHgaveat 3. nsolute + msolvent —= solution AHpy 4. (solute), + (solvent), === solution AH = AHate + AHaiva + AHaa As seen above the overall enthalpy change, A Hq is the sum of the three steps: Hain = AHaaae * AHawat * AH 13.4) Separation of the solute particles from one another always requires an input of energy to overcome thei attractive interactions. The process is therefore endothermic (AHesue > 0). Likewise, separation of solvent molecules to accommodate the solute always requires energy (Havant > 0). The thied component, which arises from the attractive interactions between solute particles and solvent particles, is always exother- mic (AHgy. < 0) ‘The three enthalpy terms in Equation 13.1 can be added together to give either a negative or a positive sum, depending on the actual numbers for the system being con- sidered (> Figure 13.4), Thus, the formation of a solution can be either exothermic or endothermic. For example, when magnesium sulfate (MgSO,) is added to water, the solution process is exothermic: AHyan ~ ~91.2 kJ/mol. In contrast, the dissolution of ammonium nitrate (NHJNO,) is endothermic: AHuan = 26.4 kI/mol. These particu- lar salts are the main components in the instant heat packs and ice packs used to treat‘2.1 The Solution Process 535 Aco FIGURE How does the magnitude of AH compare with the magnitude of AHLshert + A Houte for exothermic solution processes? separated P9925] [20% 9) Solvent aggregated Hoste dled Enthalpy, H» Enthalpy, H A Exothermic solution process Endothermic solution process 44 Figure 13.4 Enthalpy changes accompanying the solution process. athletic injuries (> Figure 13.5). The packs consist of a pouch of water and the solid salt scaled off from the water—MgS0O,(s) for hot packs andl NH,NOs(s) for cold packs. When the pack is squeezed, the seal separating the solid from the water is broken anda solution forms, either increasing or decreasing the temperature. TThe enthalpy change for a process can provide insight into the extent to which the process occurs. “= (Section 5.4) Exothermic processes tend to proceed spontane- ously. On the other hand, if AHyaq is too enclothermic, the solute might not dissolve to any significant extent in the chosen solvent. Thus, for solutions to form, the solvent solute interaction must be strong enough to make A Fnac comparable in magnitude to AHoiac + AHLent This fact further explains why ionic solutes do not dissolve in nonpolar solvents. The nonpolar solvent molecules experience only weak attractive interactions with the ions, and these interactions do not compensate for the energies required to separate the ions from one another. By similar reasoning, a polar liquid solute, such as water, does not dissolve in a nonpolar liquid solvent, such as octane (C,H). The water molecules experience strong hydrogen-bonding interactions with one another ~~ (Section 11.2)—attractive forces that must be overcome if the water molecules ae to be dispersed throughout the octane solvent. The energy required to separate the HO molecules from one another is not recovered in the form of attractive interactions between the H,O and C,H, molecules A. Give it Some Thought Label the following processes as exothermic or endothermic: (@) breaking solvent-solvent interactions to form separated particles (©) forming solvent-solute interactions from separated particles Solution Formation and Chemical Reactions In discussing solutions, we must be careful to distinguish the physical process of so lution formation fom chemical reactions that lead to a solution. For example, nickel metal dissolves on contact with an aqueous hydrochloric acd solution because the fo: lowing reaction occurs: Ni(s) + 2HCI(ag) — NiCh(ag) + Ha(g) 1132] ‘4 Figure 13.5 Magnesium sulfate instant hot pack.536 CHAPTER 19 Propetties of Solutions Aco FIGURE What i the molar mass of nickel chloride hexahydrate, NiGlo-6 H:0(s)? Nickel metal and hydrochloric add Nickel reacts with hydrochloric acid, NiCly6 1,019) emains forming NiCl(aq) and H(g). The sehen solvent evaporated solution is oF Nip, not Ni metal ‘4 Figure 13.6 The reaction between nickel metal and hydrechloic acid Is not a simple ‘dissolution. The product is NICIs-6 H,0(s),nlekel() ehleride hexahyrate, which has exactly 6 waters of hydration in the enystal lattice for every nickel in, [In this instance, one of the resulting solutes is not Ni metal but rather its salt NiCh Ifthe solution is evaporated to dryness, NiCl;- 6 H,O(s) is recovered (a Figure 13.6). Compounds such as NiCl-6 H,0(s) that have a defined aumber of water molecules in the crystal lattice are known as hydrates. When NaCl) is dissolved in water, on the other hand, no chemical reaction occurs. Ithe solution is evaporated to dryness, NaCl is recovered. Ou focus throughout this chapter is on solutions from which the solute can be recovered unchanged from the solution. 13.2 | Saturated Solutions and Solubility Asa solid solute begins to dissolve in a solvent, the concentration of solute particles in solution increases, increasing the chances that some solute particles will collide with the surface of the solid and reattach. This process, which is the opposite of the solution process, is called crystallization, Thus, two opposing processes occur in 1 solution in contact with undissolved solute. This situation is represented in this chemical equation: Solute + solvent = solution {1331 When the rates of these opposing processes become equal, a dynamic equilibrium is established, and there is no further increase in the amount of solute in solution. ox (Section 4.1) A solution that isin equilibrium with undissolved solute is saturated. Additional solute will not dissolve ifadded to a saturated solution. The amount of solute needed to form a saturated solution in a given quantity of solvent is known as the solubilitySECTION 122 Saturated Solutions and Solubilty of that solute. That is, the solubility ofa particular solute in a particular solvent is the ‘maximum amount ofthe solute that can dissolve in a given amount of the solvent at a specified temperature, assuming that excess solute is present. For example, the solubility of NaCl in water at 0° is 35.7 g per 100 ml. of water. This is the maximum amount of NaCl that can be dissolved in water to give a stable equilibrium solution at that temperature. If we dissolve les solute than the amount needed to form a saturated solution, the solution is unsaturated. Thus, solution containing 10.0 g of NaCl per 100 ml. of water at 0°C is unsaturated because it has the capacity to dissolve more solute. Under suitable conditions, itis possible to form solutions that contain a greater amount of solute than needed to form a saturated solution. Such solutions are super- saturated. For example, when a saturated solution of sodium acetate is made at a high temperature anc! then slowly cooled, all ofthe solute may remain dissolved even though its solubility decreases as the temperature decreases. Because the solute in a supersaturated solution is present in a concentration higher than the equilibrium concentration, supersaturated solutions are unstable. For crystallization to occur, however, the solute particles must arrange themselves properly to form crystals. The addition of a small crystal of the solute (a seed crystal) provides a template for crys tallization of the excess solute, leading to a saturated solution in contact with excess solid (¥ Figure 13.7). Give tt Some Thought What happens if a solute is added to a saturated solution? 537 Aco FICURE What isthe evidence thatthe solution inthe left photograph is supersaturated? ‘Amount of sacium acetate Table 13.2 all contain the polar OH group. Organic compounds with this molecu- lar feature are called alcohols. The O—H bond is able to form hydrogen bonds. For example, ethanol (CH,CH,OH) molecules can form hydrogen bonds with water molecules as well as with each other (» Figure 13.9). As a result, the solute-solute, solvent-solvent, and solute-solvent forces are not greatly different in a mixture of CH,CHOH and HO. No major change occurs in the environments of the molecules as they are mixed. Therefore, the increased entropy when the compo- nents mix plays a significant role in solution formation, and ethanol is completely miscible with water.SECTION 183 Facto AetngSokbity 599 Table 13.2 Solubilities of Some Alcohols in Water and in Hexane* sony Acbot ino HVOF (meant) : CHLCHLOH (eae) : : CHLCH,CH10H (propa) = : CHLCHLCHL.CHOH aa) on : CHCHLCHLCHCHOH pemanal) 0050 E SJCHLCH,CHLCH,CHLON (hex) —_ 00185 tapresedin malo en a 29°C They pial (nde a thenaels compl mice he sent Ta yl A. iL we SH nL x6 7 ~ or \ Hydrogen bond between ethanol molecule and water molecule Hydrogen bond between ‘so ethanol molecules ‘4 Figure 13.9 Hydrogen bonding involving OH groups. Notice in Table 132 that the numberof carbon atoms in an alcohol affects its solu bility in water. As this number increases, the polar OH group becomes an even smaller part of the molecule, and the molecule behaves more like 2 hydrocarbon. The solubility of the alcohol in water decreases correspondingly. On the other hand, the solubility of alcohols in a nonpolar solvent like hexane (Cyl) increases as the nonpolar hydeocar bon chain lengthens ‘One way to enhance the solubity ofa substance in waters to increase the number of polar groups the substance contains. For example, increasing the number of OH groups in a solute increases the extent of hydrogen bonding between that solute and water, thereby increasing solubility. Glucose (CyH,.0, > Figure 13.10) has five OH groups on a six-carbon framework, which makes the molecule very soluble in water: 830 g dissolves in 1.00 L of water at 17.5°C. In contrast, cyclohexane (CH), which has a similar structure to glucose but with al of the OH groups replaced by H, is essentially insoluble in water (only 55 mg of cyclohexane can dissolve in 1.00 Lf water at 25°C). fas no polr OF groups, = essentially insoluble in water (OH groups enhance the aqueous schubty becauce of their lity 10 hydrogen bond with H,0. Hiydrogen-bonding sites ‘A Figure 13.10 The corelation of ‘molecular structure with solubility. Chemistry and Life Fat-Soluble and Water-Soluble Vitamins period on a vita “diseases from appearing even after person has subssted fora long, lefcient diet. ‘Vitamins have unique chemical structures that affect theie solubilities in different parts of the human body. Vitamin C and the B vitamins are soluble in water, for example, whereas vitamins A. D, E,and K are soluble in nonpolar solvents and in faty tissue (whichis nonpolar). Because oftheir water solubility, vitamins Band C are not stored toany appreciable extent in the body, and so foods containing these vitamins should be included in the daily diet. In conteast, the fat-soluble vitamins are stored in sufficient quantities to keep iin-deficiency "That some vitamins soluble in waterand othersare not can be ex plained in terms oftheir structures Notice in Figure 13.11 that vitamin ‘A (eetino) isan alcohol with avery long carbon chain Hecause the OFF ‘group is such a small pat of the molecule, the molecule resembles the long-chain alcohol listed in Table 13.2. This vitamin is nearly nonpolar Thcontras the vitamin C molecule is smaller and has several OFF groups that an form hydrogen bonds with water, somewhat ike glucose ‘Related Exercises: 13.7, 13.48540 CHAPTER 19 Propetties of Solutions Only one polar group to interact with water ‘Many polar groups to interact with water Most of molecule nonpolar Vitamin A Vitamin € ‘A Figure 13.11 The molecular stuctures of vitamins A and C ‘Over years of study, examination of different solvent-solute combinations has led to an important generalization: Substances with similar intermolecular attractive forces tend to be soluble in one another. This generalization is often simply stated as “like dis- solves like” Nonpolar substances are more likely tobe soluble in nonpolar solvents: ionic and polar solutes are more likely to be soluble in polar solvents. Network solids such as, diamond and quartz are not soluble in either polar or nonpolar solvents because of the strong bonding within the soli. a Give It Some Thought ‘Suppose the hydrogens on the OH groups in glucose (Figure 13.10) were Topiaced with mathyl groups, CHs. Would you expect the water solubility of the resulting molecule to be higher than, lower than, or about the same as slucose? SAMPLE — - EXERCISE 13.1 Predicting Solubility Patterns Predict whether cach ofthe following substances is more likely to dissolve in the nonpolar solvent carbon tetrachloride (CC) or in water C Hye, NaS, HCl and ly SOLUTION Analyze We are given two solvents, one that is nonpolar (CCl,) and the other that is ‘polar (HO), and asked to determine which will be the better solvent for each solute listed, Plan By examining the formulas of the solutes, we can prediet whether they re onic or molecu lar or those that are molecular, we can predict whether they are polar or nonpolar. We can then apply the idea that the nonpolar solvent will be better for the nonpolar solutes, whereas the polar solvent willbe better for the ionic and polar solutes. Solve CH isa hydrocarbon, soit is molecular and nonpolar. Na;S0O,, a compound containing ‘a metal and nonmetals is ionic. HCI, «diatomic molecule containing two nonmetals that dif fer in electronegativity,s polar. Ir, diatomic molecule with atoms of equal electronegativiry, is nonpolar. We would therefore predict that C7Hjgand Iz (the nonpolar solutes) would be more soluble in the nonpolar CCl, than in polar FiO, whereas water would be the beter solvent for Na,SO, and HCI (the ionic and polar covalent solutes)SECTION 18.3 Factors Affecting Solubiltly 541 Practice Exercise 1 Which ofthe following solvents will best dissolve wax, which isa complex mixture ofcom- ihe ling sl he a 4 HY es we I A oy, ENN ae de I HH HH iH ae — 5 a f i ne“San, aya — lncatontcate HOH Soe racic bere? ce re cenit PeTTTT MCT iit oth, Stitt pee epee i tit | i ie wit ET “Owe EEE bdaad rhadd Pressure Effects The solubilities of solids and liquids are not appreciably affected by pressure, whereas the solubility of « gas in any solvent is increased as the partial pressure of the gas above the solvent increases. We can understand the effect of pressure on {gas solubility by considering Figure 13.12, which shows carbon dioxide gas dis. tributed between the gas and solution phases. When equilibrium is established, the rate at which gas molecules enter the solution equals the rate at which solute molecules escape from the solution to enter the gas phase. The equal number of up and down arrows in the left container in Figure 13.12 represent these opposing processes. Now suppose we exert greater pressure on the piston and compress the gas above the solution, as shown in the middle container in Figure 13.12. If we reduce the gas volume to hal its original value, the pressure of the gas increases to about twice its original value. As a result of this pressure increase, the rate at which gas molecules strike the liquid surface and enter the solution phase increases. ‘Thus, the solubility of the gas in the solution increases until equilibrium is again established; that is, solubility increases until the rate at which gas molecules enter the solution equals the rate at which they escape from the solution. Thus,542 CHAPTER 19 Propetties of Solutions Aco FIGURE If the partial pressure of a gas over a solution is doubled, how has the concentration of gas in the solution changed efter equilibrium is restored? Equilibrium Pressure is increased. Equilibrium restored More CO, dissolves 4A Figure 13.12 Effect of pressure on gas solubility, Aco FIGURE How do the slopes of the lines vary with the molecular weight ofthe gas? Explain the trend. 100 Figure 13.17) must be concerned about the solubility of gases in ther blood. Although the gases are not very soluble at sea level, their solubilities can be appreciable at deep ley ls where their partial pressures are greater. Thus, divers must ascend slowly to prevent dissolved gases from being released rapidly from so- lution and forming bubbles inthe blood and other fluids inthe body These bubbles affect nerve impulses and cause decompression sick: ness, or “the bends," which sa painful and potentially fatal condition, [Nitrogen isthe main problem because itis the most abundant gas in air and because it can be removed from the body only through the ‘espratory system. Oxygen, in contrast, is consumed in metabolism, Deep: rea divers sometimes substitute helium for nitrogen in the air they breathe because helium has a much lower solubility in bi logical fluid than N, For example, clivers working ata depth of 100 ft experiance a pressure of about 4 atm. At this pressure, a mixture of ‘958 helium and 59% oxygen gives an oxygen partial pressure of about (0.2. atm, which isthe partial pressure of oxygen in normal ai at { atm, ‘a Figure 13.17 Gas solubility increases as pressure inreases. DWvers laho use compressed gases must be concemed about the solubility cf ‘he gases in thelr bod, If the oxygen partial pressure becomes too great, the urge to breathe is reduced, CO. is not removed from the body, and CO. poisoning ‘occurs. At excessive concentrations in the body, carbon dioxide acts asa ncurotorin, interfering with nerve conduction and transmission. Related Exercises: 13.59, 13.60, 13.107 13.4| Expressing Solution Concentration The concentration of a solution can be expressed either qualitatively or quantitatively. The terms dilute and concentrated are used to describe a solution qualitatively. A solu- tion with a relatively small concentration of solute is said to be dilutes one with a large concentration is said to be concentrated, Chemists use various ways to express concen- tration quantitatively, and we examine several of these next. Mass Percentage, ppm, and ppb (One of the simplest quantitative expressions of concentration is the mass percentage of ‘a component ina solution, given by ‘mass of component in sola 100 [iL Mass of componcn total mass of soln Because percent means “per hundred,” a solution of hydrochloric acid that is 36% HCL bby mass contains 36 g of HCl for each 100 g of solution, ‘We often express the concentration of very dilute solutions in parts per million (ppm) or parts per billion (ppb). These quantities are similar to mass percentage but use 10° (a million) or 10° (a billion), respectively. in place of 100, as a multiplier for the ratio of the mass of solute to the mass of solution. Thus, parts per million is defined as mass of component in soln 10° 13.6) ppm of component vehlmneataly A solution whose solute concentration is 1 ppm contains 1 g of solute for each million (10*) grams of solution or, equivalently, 1 mg of solute per kilogram of solution. Recause the density of water is 1 g/mL. 1 kg of dilute aqueous solution has a volumeSECTION 18.4 Expressing Solution Concentration 545 very close to 1 L. Thus, 1 ppm also corresponds to 1 mg of solute per liter of aqueous solution, The acceptable maximum concentrations of toxic or carcinogenic substances in the environment are often expressed in ppm or ppb. For example, the maximum allowable concentration of arsenic in drinking water in the United States is 0.010 ppm; that is, 0.010 mg of arsenic per liter of water. This concentration corresponds to 10 ppb. Give it Some Thought A solution of $0» in water contains 0.00023 g of SO» per liter of solution. What 's the concentration of SO, in ppm? In ppb? SAMPLE EXERCISE 13.3 Calculation of Mass-Related Concentrations (a) A solution is made by dissolving 13.5 g of glucose (C20) in 0.100 kg of water. What is the mass percentage of solute in this solution? (b) A25-geampleof groundwater was found 9 conan 5. ig of" Whats the concentration of Zain prt por nlion? SOLUTION (a) Analyze Weare given the numberof grams of solute (13.5 g) and the number of grams of, solvent (0.100 kg = 100g) From this, we mus calculate the mass percentage of solute. Plan We can calculate the mass percentage by using Equation 13.5, The mass ofthe solution is the sum of the mass of solute (glucose) and the mass of solvent (water). as ghicose| 135g Solve Mase of gacose = MEE 100 = a 00g % 100 = 11.9% Comment The mass percentage of water inthis solution is (100 ~ 11.9)% = 88.19%. (b) Analyze In this case weare given the number of micrograms of solute, Because 1 gis 1x 10%, 54yg = 54% 10g, Plan We calculate the parts per milion using Equation 136. mas of sate 54x10 smassofsolute gs _ 54108 Solve ppm = X 10° = 2.2ppm ‘mats of soln 256 Practice Exercise 1 (Calculate the mass percentage of Naina slution containing 1.50 g of NaCl in 50.0 g of water. {a) 0.02919 (b)0.0300%,(¢) 0.0513%, (a) 2.91%, (e) 3.00%. Practice Exercise 2 ‘A.commercial bleaching solution contains 3.62% by mass of sodium hypochlorite, NaOCl ‘What i the mass of NaOCl in a bottle containing 2.50 kg of bleaching solution? Mole Fraction, Molarity, and Molality Concentration expressions are often based on the number of moles of one or more components ofthe solution. Recall from Section 10.6 that the mole fraction of a compo- nent ofa solution is given by moles of component Mote fraction of component = [Ties of all eomponcnts 3.71 ‘The symbol X is commonly used for mole fraction, with a subscript to indicate the compo: nent of interest Por example, the mole fraction of HCLin a hydrochloric acid solution is rep- resented as X}icy. Thus, if solution contains 1.00 mol of HC1 (36.5 g) and 8.00 mol of water (144) the mole fraction of HClis Xie, = (1.00 mol) /(1.00 mol + 8.00 mol) = 0.111546 CHAPTER 19 Propetties of Solutions ‘Mole fractions have no units because the units in the numerator and the denominator can- cal. The sum of the mole fractions of all components ofa solution must equal 1. Thus, in the aqueous HCI solution, Xjjq = 1.000 — 0.111 = 0.889. Mole fractions are very use- ful when dealing with gases, as we saw in Section 10.6, but have limited use when dealing with liquid solutions. Recall from Section 4.5 that the molarity (M) of a solute in a solution is defined as moles of solute Motarity liters of soln 138) Forexample,ifyou dissolve 0.500 mol of Na,COs in enough water to form 0.250 L of solution, the molarity of NaCOs in the solution is (0.500 mol) /(0.250L) = 2.00 M. Molarity is especially useful for relating the volume of a solution to the quantity of solute contained in that volume, as we saw in our discussions of titrations. <= (Section 4.6) The molality of a solution, denoted m, isa concentration unit that is also based Con moles of solute. Molality equals the number of moles of solute per kilogram of solvent: moles of solute ilogeams of solvent {1391 Molality = Thus, if you form a solution by mixing 0.200 mol of NaOH (8.00 g) and 0.500 kg of water (500 g). the concentration of the solution is (0.200 mol) /(0.500 kg) = 0.400 me (that is, 0.400 molal) in NaOH. The definitions of molarity and molality are similar enough that they can be easily confused. Molarity depends on the volume of solution, whereas molality depends on the ‘mass of solvent. When water is the solvent, the molality and molarity of dilute solutions are numerically about the same because 1 kg of solvent is nearly the same as 1 kg of solution, and 1 kg of the solution has a volume of about II. 1e molality ofa given solution does not vary with temperature because masses do not vary with temperature. The molarity of the solution does change with temperature, however, because the volume of the solution expands or contracts with temperature. ‘Thus, molality is often the concentration unit of choice when a solution is to be used. over a range of temperatures. Give it Some Thought It an aqueous solution is very dilute, will its molality be greater than its molarity, nearly the same as its molarity, or smaller than its molarity? saw EXERCISE 13.4 Calculation of Molality A solution is made by dissolving 4.35 g of glucose (C,P:0,) in 250 ml. of water at 25°C. Calculate the molality of glucose inthe solution, SOLUTION ‘Water hae a density of 1.00 g/mL. Analyze We are asked to calculate a solution concentration in units Plan Weuse the molar mass of GgH,:O, to convert ‘of molality To do this, se must determine the number of moles of ta moles, We use the density of water to convert mi solute (glucose) and the number of kilograms of solvent (water). __to kilograms. The molality equals the number of moles of solute Solve Use the molar mass of glucose, 180.2 g/mol, to convert grams to moles: (qlucote) divided by the number of kilograms of solvent (water. 1 mol GH 1802 gC: 0. Mol catis0, ~ (4382.00) ) = 00241 mot etts0, Because water has a density of 1,00 g/ml, the mass of the solvent is Finally, use Equation 13.9 to obtain the molality (250 mL)(100 g/mL) ~ 25.08 ~ 0.0250kg 0.0241 mol (0.0250 HO Malality of C4,0, —Practice Exercise 1 ‘Suppose you take solution and add more solvent, so that the ‘original mass of solvent i doubled, You ake thie new roluton and acid more solute, so that the original mass ofthe solute is doubled. ‘What happens tothe molality ofthe final solution, compared to the original molality? (a) tis doubled. (b)It is decreased by half, SECTION 18.4 Expressing Solution Concentration 547 (6) tis unchanged, (kt wil increase or decrease depending on the molar mass ofthe sole. (6) There is no way to tell without knowing the molar mass ofthe solute, Practice Exercise 2 ‘What is the molality ofa solution made by dissolving 365 of naphthalene (CioH,) in 425 g of toluene (C_H,)? Converting Concentration Units Ifyou follow the dimensional analysis techniques you lear convert between concentration units, as shown in Sample Exes ed in Chapter 1, you can ise 13.5. To convert between molality and molarity the density ofthe solution will be needed, as in Sample Exercise 13.6. SAMPLE EXERCISE 13.5 Calculation of Mole Fraction and Molality An aqueous solution of hydrochloric acid contsine 36% HCI by mass. a) Calculate the mole faction of HCl in the solution, (b) Calculate the molality of HC in the solution, SOLUTION [Analyze Weare asked to calculate the concentration ofthe solute, HCL, in two related concentration units, given only the percentage by mass af the saute inthe soliton, Solve (a) To calculate the mole fraction of HC, we convert the masses of HCI and ,0 to moles and then use Equation 13.7: (b) To calculate the molality of HCL in the solution, we use Equation 13.9. We calculated the numberof moles of HCL in pat (a) and the mass of solvent is 64 g ~ 0.064 kg [Notice that we can’t realy calculate the mal volume ofthe 10 g of solution, Practice Exercise 1 "The solubility of oxygen gas in water at 40°C is 1.0 mmol per liter ‘of solution. What is this concentration in units of mole faction? (a) 1.00 % 10° (b) 1.80 % 10 (¢) 1.00 10-3, (€) 1.80 x 10° (€) 555 x 107% Plan In converting concentration units based on the mass or moles of solute and solvent (mass percentage, mole fraction, and molality), ‘tis tuceful to assume a certain total mass of solution. Lets assume that there is exactly 100g of solution, Because the solution is 36% HL itcontaine 36 g of HCL and (100 ~ 36) g = 61 gof HO. ‘We must convert grams of solute (HCD to moles to calculate either iol fraction or molality. We must convert grams of solvent (HO) tomes to calculate mole fractions and t kilograms to calculate molality Tmo M0) Iago imal 365g HC ret = Goer stant =r Xue = 0.99 mol HC) Molly of I~ ‘of the solution hecause we don’t knov the Practice Exercise 2 ‘A commercial bleach solution contains 3.62% by mass of NaOCl in wate. Calculate a) the mole fraction and (b) the molality of [NaOCl in the solution.548 CHAPTER 19 Propetties of Solutions SAMPLE EXERCISE 13.6 Calculation of Molarity Using the Density of the Solution A solution with a density of 0,876 g/ml. contains 5.0 g of toluene (C-H,) and 225 g of benzene. Calculate the molarity of the solution sovvTioN Analyze Our goal is to calculate the molarity of a solution, given the Plan The molarity of a solution is the number of moles of solute di- masses of solute (5.0 g) and solvent (225 g) and the density of the so- vided by the number of liters of solution (Equation 13.8). The number miei “eth enune o fey eutn 20 ok he number of moles of solute is: foles CyHy = (5.02 CoH,)| gc, ) > O0tmel Got etearas Tae Sens eeu ete (9) weer td ee 021 ue eta ne Trcpoingth nner ean te ikem oes. (0.054 mol C;Hs) /(0.225 kg solvent) = 0.24 m. Practice Exercise 1 Practice Exercise 2 “Maple syrup has a density of 1.325 g/mL, and 100.00 g of maple A solution containing equal masses of glycerol (C;H,O,) and aera cate eae ‘water hae a density of 1.10 g/ml. Calculate (a) the molality of the molarity of calcium im maple syrup? glycerol, (b) the mole fraction of glycerol, (c) the molarity of (2) 0.017 M, (b) 0.022 M, (c) 089 M, (4) 12.6 M, () 45.4 M ‘lycerol in the solution. 13.5 | Colligative Properties Some physical properties of solutions differ in important ways from those of the pure solvent. For example, pure water freezes at 0°C, but aqueous solutions freeze at lower temperatures. We apply this behavior when we add ethylene glycol antifreeze to a car's radiator to lower the freezing point of the solution. The added solute also raises the boiling point of the solution above that of pure water, making it possible to operate the engine ata higher temperature. Lowering of the freezing point and raising ofthe boiling point are physical prop- erties of solutions that depend on the quantity (concentration) but not on the kind or identity of the solute particles. Such properties are called colligative properties. (Colligative means “depending on the collection’; colligative properties depend on the collective effect of the number of solute particles.) In addition to freezing, point lowering and boiling-point raising, vapor-pressure lowering and osmotic pressure are also colligative properties. As we examine each one, notice how solute concentration quantitatively affects the property, Vapor-Pressure Lowering A liquid in a closed container establishes equilibrium with its vapor. == (Section 11.5) ‘The vapor pressure is the pressure exerted by the vapor when it is at equilibrium with the liquid (that is, when the rate of vaporization equals the rate of condensation) A substance that has no measurable vapor pressure is nonvolatile, whereas one that exhibits a vapor pressure is volatile ‘A solution consisting of a volatile liquid solvent and a nonvolatile solute forms spontaneously because of the increase in entropy that accompanies their mixing. InSECTION 13.5 Collgative Properties 549 @ Voie sovent prices @Nonvolatie solute particos Add nonvolatile solute => => Equilibeium Rate of vaporization Equilibrium scestablished reduced by presence ‘with fewer molecules in ‘of nonvolatile solute ‘gas phase ‘4 Figure 13.18 Vapor pressure lowering. The presence of nonvolatile solute paticles in a Tiguid solvent resus ina reduction of tha vapor pressure above the liquid effect the solvent molecules are stabilized in their liquid state by this process and thus havea lower tendency to escape into the vapor state. Therefore, when a nonvolatile sol tute is present, the vapor pressure ofthe solvent is lower than the vapor pressure ofthe ‘pure solvent, as illustrated in a Figure 13.18. dealy, the vapor pressure ofa volatile solvent above a solution containing a nonvol- atile solute is proportional to the solvent’s concentration ia the solution. Ths relation ship is expressed quantitatively by Raoult’ lave, which states thatthe partial pressure exerted by solvent vapor above the solution, Poy» equals the product ofthe mole frac tion ofthe solvent, Xyipntimes the vapor pressure of the pure solvent, Prigqy: Pastn = Keates (13.10) For example, the vapor pressure of pure water at 20°C is Pigg = 17.5 torr. Imag. ine holding the temperature constant while adding glucose (C,H,,Q,) to the water so that the mole fractions in the resulting solution are Xj.4o = 0.800 and Xc,u,.0, = 0.200. According to Equation 13.10, the vapor pressure ofthe water above this solution is 80.0% ofthat of pure water: Paton = (0-800)(17.5 torr) = 14.0 tore ‘The presence of the nonvolatile solute lowers the vapor pressure of the volatile solvent by 17.5 torr ~ 140 torr = 3.5torr. (he vapor-pressure lowering, AP, is directly proportional to the mole fraction of the solute, Kea? AP = Xtc Poavean (13.1) ‘Thus, for the example of the solution of glucose in water, we have AP = XcgasoyPhio ~ (0200)(17.5torr) = 3.50 torr ‘The vapor-pressure lowering caused by adding a nonvolatile solute depends on the total concentration of solute particles, regardless of whether they are molecules or ions Remember that vapor-pressure lowering is colgative property, o its value for any solu tion depends on the concentration of solute particles and not on their kind o identity. A Give tt Some Thought ‘Adding 1 mol of NaCl to 1 kg of water lowers the vapor pressure of water more than adding 1 mol of CeH:20s. Explain. SAMPLE EXERCISE 13.7 Calculation of Vapor Pressure of a Solution Glycerin (CiH,0,) isa nonvolatile nonelectrlyt with a density of 1.26 g/ml. at 25°C. Calelate the vapor pressure at 25 °C of solution made by adding 0.0 ml of glycerin to 500.0 mi of water. The vapor pressure of pure water at 25 °C is 238 torr (Appendix B), and its density is 1.00 g/mL.550 CHAPTER 19 Properties of Solutions SOLUTION Analyze Our goal is to calculate the vapor pressure ofa solution, given the volumes of solute and solvent and the density ofthe solute Plan We can use Raoult law (Equation 13.10)10 calculate the vapor pressure of colton. The mole fraction ofthe solvent inthe soltion, aca the ratio of the numberof moles of solvent (H.O}to total males of elution (moles C,H,O, + moles H.O). Sea pemttnierite, mwoos = Gawatcaion arcs, (recut no = (oom oH) Ha Xu mol H,0 + mol C:H,0; 27.8 + 0.684 one ‘sure of water for the solution: Pao = Xx Pio = (0:976)(23.8 torr) = 23.2 torr Comment The vapor pressure of the solution has been lowered by 238torr — 23.2 torr — 06 tort relative to that of pure water. The ‘vapor pressure lowering can be calculated directly sing Equa tion 13:11 together with the mole fraction ofthe solute, CsH,0y Practice Exercise 1 ‘The vapor pressure of benzene, C,H is 1000 forrat 26.1 °C. Assum- ing Raculs wis obeyed, how many moles of a nonvelatile solute must be added to 100.0 mL-of benzene to decrease its vapor pressure bby 1004 at 26.1 °C? The density of benzene is 0.8765 /cn (4) 0.011237, (b) 0.11237, () 0.1248, (4) 0.1282, () 8765. AP = XojupPiuo ~ (0024)(238 tort) = 057 torr, Notice thatthe use of Equition 15.1 gives one more significant figure than the nam ber obtained by subtracting the vapor pressure ofthe solution from that ofthe pure calves. Practice Exercise 2 “The vapor pressure of pure water at 110° is 1070 torr. A solu- tion of ethylene glycol and water has a vapor pressure of 1.00 atm at 110°C. Assuming that Raoult law i obeyed, what isthe mole fraction of ethylene gycol inthe solution? A Closer Look Ideal Solutions with Two or More Volatile Components Solutions sometimes have two or more volatile components. Gasoline, for example, is 2 solution of several volatile liquids. To gain some un- derstanding of such mixtures, consider an ideal solution af two vola tie liquids, A and B, (For our purposes here it does not matter which \we call the solute and which the solvent.) The patil pressures above the solution are given by Raoul’ law Py — XaPhand Py — Xo and the total vapor pressure above the solution s Pc = Py = QP + Nah Past ‘A Figure 13.19 The voatle components of organic mixtures can be ‘Separated on an industrial scale in these distillation towers Consider a mixture of 1.0 mol of benzene (CqH,) and 20 mol of toluene (C:Ha) (Xba = 0.33, Net = 0267). At 20°C, the vapor pres- sree of the pure substances ate Pi, = 7Stort and Poy = 22 tor ‘Thus the partial pressures above the solution are Fen Pat (033)(75tore) (067)(22torr) = 1Store and the total vapor pressure above the liquid is Prt ~ Bhen + Pou = 2Store + Store = a0 tore [Note that the vapor is richer in benzene the more volatile compontnt. The mole fraction of benzene in the vapor is given by the ratio ofits vapor pressure to the total pressure (Equations 10.14 sand 10.15): Foon Fa ADtore Although berizene constitutes only 33% of the molecules in the sou tion, it makes up 638 ofthe molecules in the vapor. When an ideal liquid solution containing two volatile ‘components is in equilibrium with its vapor, the mote volatile com- ponent will be relatively richer in the vapor. This fact forms the basis of distillation a technique used to separate (or partially sepa rate) mixtures containing volatile components. <= (Section 1.3) Distillation is a way of purifying liquids, and is the procedure by which petrochemical plants achieve the separation of crude peteo Jeum into gasoline, diesel fuel, lubricating oil, and other products, (4 Figure 13.19). Distillation is also used routinely on a small scale inthe laboratory. 25 torr Bain vapor — = 063 Related Exercises: 13. 7, 13.68SECTION 13.5 Collgative Properties ‘An ideal gas is defined as one that obeys the ideal-gas equation =~ (Section 10.4), and an ideal solution is defined as one that obeys Raoult’s law. Whereas ideality for a gas arises from a complete lack of intermolecular interaction, ideality for a solution implies total uniformity of interaction. The molecules in an ideal solution all influence ‘one another in the same way—in other words, solute-solute, solvent-solvent, and sol- tute-solvent interactions are indistinguishable from one another. Real solutions best approximate ideal behavior when the solute concentration is low and solute and solvent have similar molecular sizes and take part in similar types of intermolecular attractions. Many solutions do not obey Raoult’s law exactly and so are not ideal. If, for instance, the solvent-solute interactions in a solution are weaker than either the so ‘vent-solvent or solute-solute interactions, the vapor pressure tends to be greater than that predicted by Raoult’s law. When the solute-solvent interactions in a solution are ‘exceptionally strong, as might be the case when hydrogen bonding exists, the vapor pressure is lower than that predicted by Raoul’s law. Although you should be aware that these departures from ideality occur, we will ignore them for the remainder of this chapter. Boiling-Point Elevation In Sections 11.5 and 11.6, we examined the vapor pressures of pure substances and how to use them to construct phase diagrams. How does the phase diagram ofa solution and, hence, its boiling and freezing points differ from that ofthe pure solvent? The addition ‘of a nonvolatile solute lowers the vapor pressure ofthe solution, Thus, in ¥ Figure 13.20 the vapor-pressure curve of the solution is shifted downward relative to the vapor-pres- sure curve of the pure solvent. Recall from Section 11.5 that the normal boiling point of aliquid isthe tempera- ture at which its vapor pressure equals | atm. Because the solution has a lower vapor pressure than the pure solvent, a higher temperature is required for the solution to achieve a vapor pressure of | atm. Asa result, te boiling point of the solution is higher than that of the pure sotvent. This effect is seen in Figure 13.20. We find the normal boiling point of the pure solvent on the graph by locating the point where the T-atm pressure horizontal line intersects the black vapor-pressure curve and then tracing this ppoint down to the temperature axis. For the solution, the I-atm line intersects the blue ‘vapor-pressure curve ata higher temperature, indicating thatthe solution has a higher boiling point than the pure solvent. ‘The increase in the boiling point ofa solution, relative to the pure solvent, depends on the molality of the solute. But it is important to remember that boiling-point atm Pressure | Solution oiling point ay “Temperature an ‘A Figure 13.20 Phase diagram illustrating boiing point elevation, The black lines show the pure solvents phase equlbtia curves, and the blue lines show the solution's phase equilibria 581552 CHAPTER 19 Properties of Solutions elevation is proportional to the fofal concentration of solute particles, regardless of whether the particles are molecules or ions. When NaCl dissolves in water, 2 mol of solute particles (1 mol of Na* and 1 mol of Cr) are formed for each mole of NaCl that dissolves. We take this into account by defining i, the van't Hoff factor, as the number of fragments that a solute breaks up into for a particular solvent. The change in boiling point for a solution compared to the pure solvent AT, = T(Golution) — T(solvent) = iKyn 13.2) In this equation, J, (solution) isthe boiling point ofthe solution, T,(solvent) isthe boiling point of the pure solvent, mis the molality ofthe solute, Ky is the molal boiling- point-elevation constant for the solvent (which is a proportionality constant that is experimentally determined for each solvent), and fis the van't Hf factor. For a non- electrolyte, we can always assume i= 1; for an electrolyte, i will depend on how the sub- stance ionizes in that solvent. For instance, i= 2 for NaCl in water, assuming complete dissociation of ions. As a result, we expect the boiling-point elevation of a 1 m1 aqueous solution of NaCl to be twice as large as the boiling-point elevation of a1 m solution of a nonelectrolyte such as sucrose. Thus, to properly predict the effect of a particular solute on boiling, point elevation (or any other colligative property), itis important to know whether the solute is an electrolyte or a nonelectrolyte. = (Sections 4.1 and 4.3) Give tt Some Thought AAsolute dissolved in water causes tho boiling point to inereaso by 0.51 °C. Doos this necessarily mean that the concentration of the solute Is 1.0 1m (m Table 13.3)? Freezing-Point Depression ‘The vapor-pressure curves for the liquid and solid phases meet at the triple point. = (Section 11,6) In ¥ Figure 13.21 we see that the triple-point temperature of the solution is lower than the triple-point temperature of pure liquid because the solution has a lower vapor pressure than the pure liqui ‘The freezing point of a solation is the temperature at which the first crystals of| pure solvent form in equilibrium with the solution. Recall from Section 11.6 that the line representing the solid-liquid equilibrium rises nearly vertically from the triple point. Itis easy to seein Figure 13.21 that the triple-point temperature of the solution i lower than that of the pure liquid, but it is also true for all points along the solid equilibrium curve: the freezing point of the solution is lower than that of the pure liquid. Latm| Pressure Vapor pressure] of pure solid solvent Solution triple point ay ‘Temperature ‘A Figure 13.21 Phase diagram illustrating freezing point depression. The black lines show the pure solvents phase equilibria cures, and the blue lines show the solution's pase equilitxiaSECTION 13.5 Collgative Properties Table 13.3 Molal Boiling-Point-Elevation and Freezing-Point-Depression Constants ‘Normal Bolling ‘Normal Freezing Solvent Point (C) KyCG/m)__ Point (‘6) ‘Water, HxO 100.0 051 00 Benzene, CH, 804 253 55 Ethanol, C3H,OH 784 in 1146 Carbon tetrachloride, 768 502 m3 (Chloroform, CHCl, 12. 363 635 KyC/m) 136 512 199) 208 468 Like the boiling-point elevation, the change in freezing point A; is directly pro- portional to solute molality, taking into account the van't Hoff factor i: AT; = j(solution) — (solvent) = —iKym [13.13] ‘The proportionality constant K; is the molal freezing-point-depression constant, analogous to K;, for boiling point elevation, Note that because the solution freezes at a lower temperature than does the pure solvent, the value of AT; is negative. Some typical values of Ky and K; for several common solvents are given in 4 Table 13.3. For water, the table shows K, = 0.51°C/m, which means that the boiling point of any aqueous solution that is 1 m in nonvolatile solute particles is (0.51 °C higher than the boiling point of pure water. Because solutions generally do not behave ideally, the constants listed in Table 13.3 serve well only for solutions that are rather dilute. For water, Kis 1.86°C/m. Therefore, any aqueous solution that is 1 m in nonvola tile solute particles (such as 1 m ClH,30, oF 0.5 m NaCl) freezes atthe temperature that is 1.86°C lower than the freezing point of pure water. ‘The freezing-point depression caused by solutes has useful applications: itis why antifreeze works in car cooling systems, and why calcium chloride (CaCl) promotes the melting of ice on roads during winter. SAMPLE aR EXERCISE 138 Calculation of Boiling-Point Elevation and Freezing-Point Depression Automotive antifreeze contains ethylene glycol, CH,(OH)CH,(OH), a nonvolatile noneec trolyte, in water. Calculate the boiling point and freezing point ofa 25.0% by mass solution of ethylene glycol in water. SOLUTION ‘Analyze We are given that a solution contains 25.0% by mass ofa nonvolatile, nonelectrolyte sol- ute and asked to calculate the boiling and freezing points ofthe solution. To do this, we need t0 calculate the boiling-point elevation and freeing. point depression Plan To calculate the boling-poiat clevation and the freczing-point depression wsing Equations 12 and 13.13, we must express the concentration ofthe solution as molality. Lets assume for convenience that we have 1000 g of solution. Because the solution is 25.0% by wnass ethylene elycol. the masses of ethylene glycol and water in the solution are 250 and 750, respectively Using these quantitis, we can calculate the molality ofthe solution, which we use with the molal boiling-point-elevation and freezing-point-depression constants (Table 13.3) to calculate A, and AJ, We add A, to the boiling point and A, tothe freezing point of the selvent to obtain the boiling point and freezing point ofthe solation, y( 1000 5 1,0" kg H,0 Solve ‘The molality of the solution i calculated as fllows: eae mol CHE G2 gCH 553