chapter 3 t Chemical Concepts: Expressing Quantities and Concentrations 1 this chapter. we explore a number of concepts and skills that are impor- ‘ant in analytical chemistry. Although you have probably studied these top. ics im other chemistry courses, you should find it fruitful to refresh these \eas in your mind before proceeding. We begin by presenting the SI system of anit, the important distinction between mass and weight, and the mole. We then svestigate the numerous ways of expressing solution concentration and present ihe basics of chemical stoichiometry 3A SOME IMPORTANT UNITS OF MEASUREMENT 3A-1 St Units Scientists throughout the world are adopting a standardized system of units now ns the International System of Units (SI). This system is based on the ‘sen fundamental base units shown in Table 3-1. Numerous other useful units, ‘uch a volts hertz, coulombs, and joules, are derived from these base units,! Prefixes are used with these base units and other detived units to express fhull or large measured quantities in terms of a few simple digits. As shown in Tile 3-2, these prefies multiply the unit by various powers of ten. For exam- Al, the wavelength of yellow radiation used for determining sodium by flame Ahotometty is about $.9 % 10-7 m, which can be expressed more compactly as 54 nm (nanometers); the volume of a liquid injected onto a chromatographic Sum is often roughly 50 x 10-*L or $0 ge. (microliters); or the amount of ime in some computers is about 64,000,000 bytes or 64 Mbytes (megabytes) 'n this course, we often determine m (tement For such measurements, 1 milligrams (mp) amount of chemical species from mass metic units of kilograms (kg), grams OF micrograms (yg) are used. Volumes of liquids are mea- SO may be : definitions of SI base unis, conversion factors, and fundamental con {undo the National niu of Standards and Tecology (NIST) Word Wide Web I ppt : PPh nist pov/ewy index. him liste acronym forthe Fresch “Syste International Unites,” ‘The Angstrom unit, A, is a non-St unit of length his widely sed to expess the wavelength of vet shot radiation suchas Xeays(1 A= 0.1 nm = 10°% ‘Typed Xreition sine rage of 4 wi0A 611 Chemical Concepts Chapter 3 Impeeta 62 Table 3 ee “Abbreviation | | Physical Quant kg ~ kilogram s Mass ae Length second . Time kelvin Temperature an Amount of substance ampere Flecticcurtent me Tuminousimensity angel — Table 3-2 Prefixes for Units refx Abbreviation Multiplier _ ive G 10? meg M 10° ilo 10° This French postage stamp commemorates wl k 10" the Meter Comentn of TK7S The simp eck 4 Shows some signatures from he Tel af cent c 0? ‘the Meter, the seven SI units. and the defini m Ww? tom ofthe meter a 1,650,763 73 wave ul 10-* leaner at ene kp ‘ 10 ton-86 Since the samp wis sued in 1975, ‘ the meter has been redefined as the distance e 0 . that light wrayels 0s vacuum during f 10! a 0 1/209,792,458 ofa second me unis of er), miiliters (mL), and sometimes microliters (ul). TM 10 omar cat Nat defined as exactly 10° m?. The milliliter is defines 3A-2 The Mole The mole (mol) is the $1 unit associ 1 for the amount of a chemical species. It is al¥a® ed with a paces reprevcn a orm and is Avogadro's number (6.022 * 10) tas in grams of one meg, LorMUla. THE molar mass fof a substance is summing the omic Ins i i Substance. Molar masses are calculated bY ‘or example, the molar ns All the elements appeari ‘cal form: ‘molar mass of formaldehyde Hone in a chemical f0 z mete 12.0 o1CH,O * more + ROHL, Oe. Limes mol CH,0 ~ motff + met 160g mol CHO” Reto ~ 300 mol CHO M,63 3A Some Important Units-of Messiremenr Feature 3-1 sys important to understand the diflerence betWecn mass and weight. Mass yan in Distinguishing bet ant measure of the amount of matter in an object. Weight is the force of atraction Mass and Weight Merween an object and its surroundings, principally Earth, Because gravitational at. {ction varies with geographic location, the weight of an object depends on where em weigh it. For example, a crucible weighs less in Denver than in Atlantic City (both yes are at approximately the same latitude) because the attractive force between the SMeible and Earth is smaller atthe higher altitude of Denver. Similarly, the crucible soghs more in Seattle than in Panama (both cities are at sea level) because Earth i ‘Smewhat flattened at the poles, and the force of atraction increases measurably with Intitude. The mass of the crucible, however, remains constant regardless of where you measure it Weight and ma are related by the familiar expression W= mg where W is the weight of an object, mis its mass, and g is the acceleration due to grav iy. This equation is one form of Newton's second law, which is normally written as F = ma. Inthis instance, the weight of an object W is the force F, and the acceleration due to gravity g corresponds to a in Newton's law: ‘A chemical analysis is always based on mass so that the results will not depend on locality. A balance is used to compare the weight of an object with the weight of one ‘or more standard masses. Because g affects both unknown and known equally, the mass of the object is identical to the standard masses with which it is compared. ‘The distinction between mass and weight is often lost in common usage, and the process of comparing masses is ordinarily called weighing. In addition, the objects of known mass as well as the results of weighing are frequently called weights. Always bear in mind, however, that analytical data are based on mass rather than we Therefore, throughout this text we will use mass rather than weight to describe the amounts of substances or objects. On the other hand, for lack of a better word, we will Photo of Edwin “Buzz” Aldrin taken by Neil ‘Asmstrong in July 1969. Armstrong's ceflee: tion may be seen in Aldrin’ visor. The suits worn by Armstrong and Aldrin during the Apollo 1 mission to the Moon appear to be use the verb weigh to describe the act of determining the mass of an object. Also, we will occasionally use the term weight to describe the standard masses that are used in quite massive, But because he mass of the : Joon is only 1/81 that of Earth and the ac weighing. celeraton due to gravity is only 1/6 that on Earth, the weight ofthe suits on the Moon was only 1/6 of their weight on Earth, The amass ofthe suits, however, was ideaical in 1nd that of glucose C,H);0, is both locations. Photo sortesy of the mote molt National Aeronautics and Sp Mey.,o, = —OBE_ , 1208 , 12 mek _ Administration mol CoH;,0, ~ met€ mol CoHi20¢ Smo 16.08 mol C,H,,0, ~ morO = 180.0 g/mol C,H,,0, us, 1 mol of formaldehyde has a mass of 30.0 g and 1 mol of glucose has a Mass m isan invariant measure of the WSs of 180.0 g. amount of mater. Weight W isthe fore of {grvitatonal attraction between that mater and Earth ‘3° The Millimole Retimes itis more convenient to make calculations with millimoles (mmol) t than moles, where the millimole is 1/1000 of a mole. The mass in grams Yeamol = 10-98 i millimole of a substance, the millimolar mass, is likewise 1/1000 of the mass,64 Feature 3-2 ‘Atomic Mass Units and the Mole CHALLENGE: Show that the folowing veresting and wsful relationship cemrect I moe of ato mass its = 16.022 « 10? amo = 1 gram. ‘A mole of a chemical species is 6.022 %. 10% atoms, molecules, ons, electrons, ion pais, or subatomic particles, “The number of moles n, of a species X of molar mass M, is given by ox smal X ‘mol X ee ‘The numberof millimoesis given by BX _ mmol X mmol = mmol * gx {In making calculations ofthis kin, you should include all wits as we do throughout this chapter This practice often reveals er tors in setting up equations j ofthis te sige ane back over OF TNS TeX ¥ , ed in the table inside Tare atomic mass in, the len omic mass writs (2 or dato C carbon isot wai sof nce is the UC ca Pe, ick definition 1/12 0F the mage of e refere ve in which the 1 cae > amu. Ths, the ame IS ya defined as the Ass in grams ig. Likewise, the molar nay “The masses for ative masses in erm a relative 12 is then exactly 12 1 Cat “ . xt is the mass in grams of 0. units. iS, the : of any other lem ne atomic mass of the ment in 29 anit TIA zg rere equal gen 15.9994 aS molar mass is 15.9994 » amass of naturally 0° | Approximately one mole of each of several diferent elements. Clockwise [as of several different elements. Clockwise from the uppe kt ¥¢ sit sete ls 7 tcp admin 20 go head ts ga chips, 52 of chromium chunks, and 32g of sulfur powder. in the phot be ‘lane o Sm Photo by C.D. Winters. Pans Tage 9 eee 3A-4 Calculatin 1g the Amount of in Moles or Milimoles Substance ‘The two example ‘amples that follow illustrate how the number of moles oF millimoles of a species can be det ; termined . Chemically related epee ted Hom Hs mass in grams or from the ms Example 3-1 Determine the numbe; san t of mok wles of benzoic acid prea bred roles and millimoles of benzoic acid ( = | If we use HBz to repre has a mass of 122.1 g. Thus 1 sent benzoic aci , Acid, we can write that 1 mol of HB amount of HB = 2.00 g Bg x —| mol HBz, 122.1 gyygg ~ 020164 mol HBe3B Solutions and Their Concentra ro obtain the number of millimoles, we divide by the millimolar mass (0.1221 g/mol). That is, amount HBz 16.4 mmol HBz Example 3-2 Determine the mass in grams of Na* (22.99 g/mol) in 25.0 g of NazSO, (142.0 g/mol) ‘The chemical formula tells us that 1 mol of Na;SO, contains 2 mol of Na*. That is, amount Na* = no. moLNexS0; x 2201 Na mol Ne SO; ‘ofind the number of moles Na;SO, we proceed as in Example 3-1: mol NazSOx amount Na;SO, = 25.0 gNex8@; X Se mount Na: eNeS0:X Ty : Combining this equation with the first leads to 1 BSO% m o amount Na* = 25.0 ge,SG; x DoNeOe , _2mol Na 142.0 NaS; mol. NezSO; To obtain the mass of sodium in 25.0 g Na;SO,, we multiply the number of moles Na” by the molar mass of Na*, or 22.99 g. That is, 22.99 g Na” no. moHNat x ——S mol mass Na Substituting the previous equation gives the number of grams of Na*: 1 mob NesSO; mass Na* 5.0 gNex80: * 799.0 g Nae 2 2.99 g Na* mola”, 22.998 NA" _ 6 1g nar 3B SOLUTIONS AND THEIR CONCENTRATIONS 3B-1 Expressing Solution Concentrations Chemists express the concentration of solutes in solution in several ways. The ‘ost important ways are described in this section. Molar Concentration The molar concentration of a solution of a chemical species X is the number of ‘oe ofthe solute species that is contained in one liter ofthe solution (not one er of the solvent). Molar concentration, or molarity M, has the dimension® Mol L_'. Molarity is also equal to the number of millimoles of solute per 65 Molecular model of benzoic acid. Benzoic acid occurs widely in nature, particularly in berries It finds broad use as a preservative in foods, fats, and fruit juices; as a mordant for dying fabric; and asa standard in calorimetry and in acid/base analysis.66 Feature 3-3 Another Approach to Example 3-2 Chapter 3 tnyportant Chemical Concepts ‘You may find it advantageous to use the factor-label method to solve problems of y type we have been discussing. In this method, we write out the solution toa poen Ups we hae een pe ofeach seceding facsimile ew np rnumerator ofthe preceding one until we arrive atthe units of the answer For examy ie aa pe aawerisexpesed in nis of Na" and he HER ay x ree nit of ga SO, Ts, we can wre ‘mol Na;SO. x mol NasSOu_ 142.02 NaS, 25.0 [Link] First eliminate mol Na,SOx if the number moles of solute is m, and the volume of milliliter of solution. Thus, jven by the following equation. the solution is V, then the molar concentration ¢i8, a 3-1} 7 GB) no, mol solute no, L solution ‘no. mmol solute j no, mL solution Example 3-3 a Gates the maar conctation of etanol in an aqueous souton tat tains 2.30 of CaH,OH (46,07 g/mol) in 3.50 L of solution tae molar ithe qumer of mole of solute per iter of solution, Plt iit be needed the number of moles of solute and the volume of the solution w irc wotume Vis given as 350 L, so all we need to dois 10 convert the MASS. responding number of moles ethanol t0 the 1 mol HOH eqon = amount CHOW = 23026 0H X 35> coor HOM 46.07 CHOW = 0,04992 mot C,H,OH ‘ro obtain the molar concentration, at We divide the numberof moles of Thanol by the volume. Thus, “Meson _ 0.08992 mol CH,OH v 3501 = 0.0143 mol C,HOH/L = 0.0143 Manalytical Molarity. The analytical molarity of a solution gives the gota umber of moles of a solute in 1 L of the solution, or alternatively, the total umber of milimotes in 1 mL. That is, the analytical molarity specifics a recipe by which the salution can be prepared. For example, a sulfuric acid Solution thet tus an analytical concentration of 1.0 M can be prepared by dissolving 1.0 mol, 0198 g, of H;SO, in water and diluting to exactly 1.0 L. Equilibrium Molarity. The equilibrium molarity, or species molarity, ex- presses the molar concentration of a particular species in a solution at equilib. rium. To determine the species molarity, it is necessary to know how the solute tehaves when it is dissolved in a solvent. For example, the species molarity of H,SO. in a solution with an analytical concentration of 1.0 M is 0.0 M because the sulfuric acid is entirely dissociated into a mixture of HO", HSO,., and S02 ions; there are essentially no H;SO, molecules as such in this solution. The equilibrium concentrations and thus the species molarities of these three ions are 1.01, 0.99, and 0.01 M, respectively. Equilibrium molar concentrations are usually symbolized by placing square brackets around the chemical formula for the species, so for our solution of H,SO, with an analytical concentration of 1.0 M, we can write {H,S0,] = 0.00M —[H,0*} = 101M [HSOz]=0.99M [SO] = 0.01M Example 3-4 Calculate the analytical and equilibrium molar concentrations of the solute species in an aqueous solution that contains 285 mg of trichloroacetic acid, CLCCOOH (163.4 g/mol), in 10.0 mL. Trichloroacetic acid is 73% ionized in water As in Example 3-3, we calculate the number of moles of Cls;CCOOH, which we designate as HA, and divide by the volume of the solution, 10.0 mL. or 0.0100 L. Thus, LgHA 1 mol HA 1000 mgHA ” 163.4 gHA = 1.744 x 10°? mol HA amount HA = 285 mg HA x The molar analytical concentration, cya, is then L744 10 mol HA 1000 mE _ mol HA 10.0 mt. ~OTL 0.174 1.174 M In this solution, 73% of the HA dissociates, giving H* and A’ HASH’ +A ‘The species molarity of HA is then 27% of cya- Thus, 0.174 x 0.27 [HA] = en, x (100 — 739/100 = 0.047 M larity of A> is equal to 73% of the analytical concentration of 67 Analytical molarity isthe total number moles ofa solute, regardless of its chemi ‘eal sate in one liter of solution. The ana Iytical molarity describes her a solution ‘of a given molarity can be prepared Equilibrium molarity, of species molarity fs the molar concentration of a partioular species in a solution at equilibrium. Some chemists prefer to distinguish between species and analytical concentrations in 3 diferent way, They use malar concentration for species concenteation and formal con ‘conration (for analytical concentration Applying this convention to our example wwe can say thatthe formal concentration of H.$0, is 10 F, whereas its equilibrium mo- Jar concentration is 0.0 M Inthis example, the analytical molarity of W580, is given by uso, = [SOF] + [HSO;] because these ute the only two sulfate- containing species in the solution,Chapter 3 pt cei ‘oncepts 68 motHA® _ 9.127M [Link] A _ ba x0. 174— (81 = 700 moHH L H* is formed for each wey = (ay = 027M __—— 1.108 M BaCl, from Bi Deseribe the preparation of 2.001 of 0. (244 g/mol). "To determine the oumber of BFaTS of solut Molecular mode! of trichloroacetic aid. The 4 wetenlorcetc acidis 2-00 L WE NOE that 1 mol of the dihydrate ye jution we will need mole A, we ean also write Because one mole H te to be dissolved and diluted to ‘ds 1 mol of BaCls. Therefor, rater sng acidity roatly ascribed tthe inductive effect ofthe {0 produce this sol ‘ac norne atoms atached 9 the end of 0 ol Bay 240 the molecule opposite the acidic proton 200% x 118 0.216 mol Bal; 2H;0 Electron density is withdrawn away fom the ‘earborylate group 50 that the trichlorou: cre ano thats formed when the acid i> 21,0 is then “The mass of BaChs* 3 -2H,0 (244.3 g BaCl*2H:0_ = 52.8 g BaCl;-2H.0 Senintes is stabilized. The acd is used in sce precipitation and deratalogal partons forthe removal of undesirable 0.216 mol Bach 2H30 * Skin growths. Dissolve 52.8 g of BaCly2H,0 in water and dilute to 2.00 L. Example 3-6 Describe the preparation of 500 mL of 0.0740 M CI solution from solid BaCl,-2H,0 (244 g/mol) 0.0740 mob eT say 2H;0 0. we 0500 u x 1imot BaCls:2t amass BaCl-2H,0 = 2° zg 2 moter” “The number of moles ofthe species Ain 8 x 244.3 g BaCl*2H,0 solution of Ais gives bY ‘mol BaCl,-2H,0 Xn = 452g BaCl;-2H;0 were Vis the welume of the soluion isso! jssolve 4.52 g of BaCly:2H,0 in water and dilute to 0.500 Lor 500ml _ | _ Deu nO ee percent Concentration Chemists frequently express concentrations in but pease comet ns in terms of percent (parts Pet se tron, pct sae ae i owiods Hon ‘of a solution can be expressed in several ways. Three comm0® Weight solute. 190% weight percent (W/) = ighr son lution volume solute Yolume solute. 100% en weight solute, & Weight solute, 8 100% volume soin, ml- volume percent (v/v) = weight Volume percent (w/v) =SB Solutions and Theis Concentrations Note that the denominator in each of these expressions refs t0 the solution rate than tothe solvent, Note also that the fist wo expressions do nt depo on the units used (Provided, of course, thatthe numerator and denominace expressed in the same units) Inthe third expression, units must be defined be- cavse the numerator and denominator have different units that do not canes, Or the three expressions, only weight percent has the virtue of being temperature- independent. ‘Weight percent is fréquently used to express the concentration of commercial aqueous reagents. For example, nitric acid is sold as a 70% solution, which sans that the reagent contains 70 g of HNO, per 100g of solution (se Example 3-10), Volume percent is commonly used to specify the concentration of a solution prepared by diluting a pure liquid solute with another liquid. For example, a 5% ‘queous solution of methanol usually describes a solution prepared by diluting 5.0 mL of pure methanol with enough water to give 100 mL, Weight/volume percent is often used to indicate the composition of dilute aqueous solutions of solid reagents. For example, 5% aqueous silver nitrate often refers to a solution prepared by dissolving 5 g of silver nitrate in sufficient water to give 100 mL of solution, To avoid uncertainty, always specify explicitly the type of percent composi- tion being discussed. If this information is missing, the user must decide intu- itively which of the several types is involved. The potential error resulting from a ‘wrong choice is considerable. For example, commercial 50% (w/w) sodium hy- droxide contains 763 g of the reagent per liter, which corresponds to 76.3% (w/v) sodium hydroxide. Parts Per Million and Parts Per Billion For very dilute solutions, parts per million (ppm) is a convenient way to express concentration: mass of solute pm = SS OF Sele 5 108 ppm ven “Mass of solution po Where rym is the Concentration in parts per million. Obviously, the units of ‘eight in the numerator and denominator must agree. For even more dilute solu- ions, 10° ppb rather than 10° ppm is used in the foregoing equation to give the fesults in parts per billion (ppb). The term parts per thousand (ppt) is also en- countered, especially in oceanography. Example 3-7 [Kha isthe molarity of Kina sotution that contains 63.3 ppm of KaFe(CN), 29.3 g/mol)? “ause the solution is so dilute, it is reasonable to assume that its density is 8/mL, Therefore, according to Equation 3-2, 633 ppm K,Fe(CN), = 63.3 mg KsFe(CN),/L. 199 69 Weight percent would be more properly called mass percent and be abbreviated ‘mm. The term weight percent is so widely used in the chemical literature, however, that we will use it throughout this text, You should always specify the type of Perceat when reporting concentrations inthis way. 1 A handy rule for calculating concentration Jn pars pc milion that ode gue | ou sctions whos easiest po | rately LOD gL, 1 ppm = 1.009 | mais | sass solute (mg) be = 6 m» ~ “lume station (L) For prs per billion, 1 pp = 1 g/L ms IMB soppyTe most well-koowa which ‘sth negative lori othe 0 nydrochlorie {C1 Hydrogen chloride “of eteronuceat diatomic is extemel So}Nble i function is 9H, ith of (10° is prepared of the ecules sssocat 0 ci, which com Chapter 3 ol KF o(CN)o_ 309.3 pK Fe(EN 1,922 x 104M (ENT, , Amol k ution-Dituent Votume Ratios a dilute solution is sometimes specified in terms of the late used in dung fed solution and the volume ‘of solvent to be A} from that of the later BY @ colon, Ths, @ mn contains if water for each volume of ‘concened ii This method of notation iS frequently ambiguous in hat He lays obvious to the reader Moree, re volume with three ‘volumes. diluent ratios sol “The composition of ‘of a more concentra SThe volume ofthe forme is SePHIAT 1:4 HCI solutio four volumes hydrochloric acl ‘Sontration ofthe oFiginal solution 1S not Sider some circumstances 1:4 mean dilute 07% Meh uncerantes, you should avoid VINE solution- Because 0 p-Functions Scientists frequently express the concentration of a species i fer" of its function, or p-value. The p-value #6 the negative base-10 logarithm (log) oft talar concentration of that species. T ‘nus, for the species X, pX = = log [X] vf allowing pevalues offer the advantage 1°" hhown by the following examples, sre orders of magnitude to be expres Ass Concentrations that vary aver ten! oF M0 terms of small positive numbers, Example 3:8 Cateulae the p-value for each fon in and Sed 10 * Min HCL pH = log [H,0"] = ~log 64 x 10°) ymin dl 4 solution that is 2,00 X10 1 we write pNa = ~log (2.00 X 10°) = 2.699 concentration is give tion is given by the sum of the cof To obtain The total Cl " me wal centrations © [ch] = 200 x 10M + 5.4 x 104M |= 200 > 10-9 M + 0.54 % 10° M pCl = —log 2.54 x 10°? = 2.595 sax 10M —l| f I } 3B Solutions and Test Conecnration Note that in Example 3-8, and in the one that follows, the results are rounded according to the rules listed on page 144 nes Example 3-9 Galculate the molar concentration of Ag iN a solution that has a pAB of 6.372 pAg = ~ log [Ag’] = 0372 log [Ag’] = ~ 0.372 [Ag’] = antilog (~ 6:3 4.246 10) 3B-2 Density and Specific Gravity of Soluti red in the ume, whereas its specific grav al volume of water at 4°C Density and specific gravity are often encounter The density of a substance is its mass per unit vol iy is the ratio of its mass to the mass of an equ Density has units of kilograms per liter or grams per milliliter in the metric sys fem. Specific gravity is dimensionless and so is not tied to any particular spsterm wT unite For this reason, specific gravity is widely used in deseribing items of Figure 3-1. which is the label trom a bottle of feagent-grade hy ‘commerce, BAKER SAF-T-DATA® System amity meacrOy (2) 83 siademath ohh TBee © [Link] tne. Prispaurg my oases SA MRE! rae hydrochloric acid Note that he SPECIE Figure 3-1 Label {rom a bottle of reagent {0 80°F is specified om the label. Density is the mass of substance per it n St units, density fs expressed in nis of kg/L or alternatively g/m Speci gravity substance of water 36.5-38.0% is the ratio ofthe mass of tothe mass of an equal volume 9535-03 Acid, = porate “— "BAKER ANALYZED'* Reagent == a} g 8 a om I q 2 == ee con = = i | 3 DANGER! Se Poon 5 eae Lor z99009 SS, = _anvee ehtabir SWALLOW Cr cae HesmAes ortonion SET be + So NE See rams ates | Sa ca pe"e = Raiser gomeea eae | fetes ao => os pace ‘Rosie afar aries eee te = ee ee ccrmnmere | Seren i = Se nl Secgene siters c, See rac) Soe Serireeessen | ois 2 o£ 5 tee crencaney | Sat. 8 £ om aed necia nn Tmatoenstencs yea rere ar # = Ses kerndarg reat neataenen_| Bats oa CAF Boker MEUTRASORD® or TEAMS Low Nee 8! = tends to be lene tha SEER ager rte ow sno "NOTE! Ay teh cement =_— : ve temperature range of 609 Cheical COMP apter 3 Imp er is approxi ow rensity of Water iS aPPFOXimatey since the deenghout this Xt. We we the 72 : ses this poin drchore ai pe metic ser 1,00 g/mL. ae if gravits interchangeab!s terms density and PC Example 310 5.0 gimol) in a solution thi has atelate the molar concentration of HNO, (634 gm sinc rites of Commercial Calculate con 70% HNO (8 “ene l Scetated Acs a BS = speci te a oF ud per liter of €OM i Concentra ne Fetus first cal : / Concentration oon > 10" . z Regent juno, __LAzkEseOBe gseugent 7 ~~ Lreagent kgrengemt peices i reagent g-roager ‘Amma yo Oe | spt gHNO, wrimdies y re yeroftone er ws us Then scons Nic acid 7” ae 994 gHNO: _L mol HNOs 5.8m 16M = 1" 187 cso. = TP reagent 63.0 g HNO} L reagent md ° © noi Oe acid ~ 860 un sultricxcd 965 1 gyarnple 3.11 a ‘of 6.0 M HCI from a concentrated solution equation 3.3 can be used with Land mol/L ‘or ml. and mmol/l. Thus, Le Describe the preparation of 100 ml that has a specific gravity of 1.18 and is 37% (w/w) HCI (36.5 g/mol). Proceeding as in Example 3-10, we first calculate the molarity of the com centrated reagent. We then calculate the number of moles of acid that We for the diluted solution. Finally, we divide the second figure by the first 0 tain the volume of concentrated acid required. Thus, to obtain the molarity of the concentrated reagent, we write fyq = IS 10 eteegemt 37 BE mol HCl _ yt Lmmagoot 100 gseegent “36.5 gHEl ‘The number of moles of HCI required is given by ‘no. mol HC = 14 ik S.0mot . 00 mt, x EE x SO mol HCL _ 9549 mel i inally, to obtain the volume of concentrated reagent, we write vollconed reagent = 0,600 moLHeT x LL reagent_ 12.0 moH#CI = 0.0500 L or 50.0 mL Thus, dilute 50 ML of the concentrated reagent to 100 mi The solution Which we will be Ex*™Ple 3-11 is based i wile wing counlese times,” M fllowing useful relationshiPs ¥, whee 0k om he * Cant = Va X ey 6) € left Ste the volume and molar concentration of *°""73 3C Chemical Stoichiometry centrated solution that is being used to prepare a diluted solution having the yolume and concentration given by the corresponding terms on the right, ‘The basis of this equation is that the number of moles of solute in the diluted solution must equal the number of moles in the concentrated reagent. Note that the Jong as the same units ate used for both 18 oF lite volumes can be in mill solutions, 3C CHEMICAL STOICHIOMETRY Swoichiometry is defined as the mass relationships among reacting chemical = son the wla- species. This section provides a brief review of stoichiometry and its applica. PARE wolcomery oft wot ls tons to chemical calculations ens | ome enton 3C-1 Empirical Formulas and Molecular Formulas An empirical formula gives the simplest whole-number ratio of atoms in a chemical compound. In contrast, a molecular formula specifies the number of atoms in a molecule. Two or more substances may have the same empirical for- mula but different molecular formulas. For example, CH,0 is both the empirical and the molecular formula for formaldehyde; itis also the empirical formula for such diverse substances as acetic acid (C;1,0;), glyceraldehyde (CsH,O,), and slucose (C,H),0,), as well as more than 50 other substances containing 6 or fewer carbon atoms. The empirical formula is obtained from the percent compo- sition of a compound. In addition, the molecular formula requires a knowledge of the molar mass of the species. A structural formula provides additional information, For example, the chem- ically different ethanol and dimethyl ether share the same molecular formula C3H,O. Their structural formulas, C3HsOH and CH;OCH,, reveal structural dif- ferences between these compounds that are not discernible in the molecular for- ‘mula that they share. 3C-2 Stoichiometric Calculations A balanced chemical equation is a statement of the combining ratios, or stoi- chiometry (in units of moles), among the reacting substances and their products. Thus, the equation 2Nal(ag) + Pb(NO,)s(aq) = Pbla(s) + 2NaNO\(aq) ‘Often the physical state of substances ap- indicates that 2 mol of aqueous sodium iodide combine with 1 mol of aqueous 2 ee ee waste J . tes (4) (0 (9-0 (ag), wich eer to ‘a iat to produce mol of solid lead iodide and 2 mol of aqueous sodium sg . Fespectve i, Example 3-12 demonstrates how the mass in grams of reactants and products states respecnely "4 chemical reaction are related, As shown in Figure 3-2, a calculation of this nd aqueous solution nwa ct advantageous to depict the reaction in terms of chemical compounds, If we wish 10 focus "Acting species, the net ionic equation is preferable 21> (ag) + Pb (ag) = POA)ant Chea CONEEPS Chapter 3 Imp 74 ap ae i) 2 , Moles ass oles [=F . Maltiply by le Multiply bY yby Diem, Sojneie —_emes ometric calculations (1) When the mass of eae- 1+ making stoichi re 3-2 Flow dagam 0 mE humber of moles using the molar mas. 2) i Fe give, the mass frst converted t0 the at mera ven be chemical equation fr the reaction is then used to find the am. Perea ane ata tat combine withthe origin) substance or the numberof mos of prec that os) Finally he mass of heater reactant of the product is computed from ts mo- lar mass. type isa three-step process involving (1) transformation of the known nrass of a substance in grams to a corresponding number of moles, (2) multiplication by a factor that accounts for the stoichiometry, and (3) reconversion of the data in moles back to the mettic units called for in the answer, Example 3-12 (a) What mass of AgNO; (169.9 g/mol) is needed to conv Wh r ert 2.33 g of NajCOs i 6.0 ginal) to Ag,CO3? (b) What mass of Ag,CO, (275.7 g/mol) will be (@Na:COs(ag) + 2AgNOx(ag) > AgsCOXG) + 2NaNOs(ag) Step 1: Maco, = 233 gageo; x [Link] _ 1060 5 = 0.02198 mol Na,CO, Step 2: 2: The balanced equation reveals that "avo, = 002198 molNaz60; x 2 ol ABNOs_ - | molNas€05 veces. {1.04396 mol AgNO, - stoichiometric facto 1 is 2 mol AgNO, )/(1 ‘mol Na,CO,). Step 3: Man, = ‘wo, = 0.04396 mol Agno; x 169.9 g ANOs oe ones = 7.47 g AgNO, = Moco, = 0.02198 mol ™ rec, = 0.02198 2 mol-Ag:co; x 275.7 8 [Link], = 6.06 3° elapse ___ BABCO, Ri3C Chemical Stoichiometry ~ Example 3-13 - _ What mass of [Link], (276 g/mol) is formed when 250 mL. ol AgNO; is mixed with 50.0 mL of 0.0800 M Nasco,? Mixing these two solutions will result in one bie outcomes, specifically (and only one) of three possi- 1. An excess of AgNO, will remain after reaction is complete. 2 An excess of NaCO, will remain after reaction is complete 3. An excess of neither reagent will exist (that is, the number of moles of NazCOs is exactly equal to twice the nimber of moles of AgNO. ). As a first step, we must establish which of these situations applies by calculat- ing the amounts of reactants (in chemical units) available at the outser. ‘The initial amounts are 1LAgNO; 0.200 mol AgNO, 1000 ml. AgNO; LABNO; = 5.00 x 10°? mol AgNO, 1 LNax€05 0.0800 mol Na,CO, "waco, = 50.0 mL Ney€O; x —————*EO3_ 0.0800 mol Na;COs_ " LNa€0; 1000 mL Neg€05, 7 = 4.00 x 10°? mol Na,CO, Because each CO}” ion reacts with two Ag* ions, 2 x 4.00 x 10- 8.00 x Since we have insuffi- Ag:CO, produced will 10° mol AgNO is required to react with the NaCO,, ient AgNO, situation (2) prevails and the amount of be limited by the amount of AgNO, available. Thus, [Link], woe we x Lmelr€05 276. 48,00, = 0.690 Ag,Co, a Gample 3-14 What will be the molar analytical concentration of N duced when 25.0 mL. of 0.200 M AgNO, NaxCo,? ax No, have seen in Example 3-13 that formation of 5.00 X 10°. mol of ABNOs will 1 quite 2:50 * 10°* mol of Na;COs. The number of moles of une Teacled Na,CO, is then given by ‘aC, in the solution pro- is mixed with 50.0 mL of 0.0800 M 00 X 10-* mol Na;CO, = 1.50 X 10-3 mol Na;COs ‘molarity is the number of moles Na;COs/L. Thus, 1.50 x 10~* mol Na,Co, (500 +250) wai: 8; definition, the nao, 0.0200 M Na,CO, |ee 76 Chapter 3 3D QUESTIONS AND PROBLEMS 31. Define *(a)millimole (b) molar mass “(6 millimolar mass, (4) parts per million 3-2, What isthe difference between species molarity and analytical molarity? 3. Give 10 examples of units derived from the funda mental base ST units, 3-4. Simplify the following quantities using a unit with an appropriate prefix say 25% 108 Hz (by 372 10g Me) 8.43 > 10° mot (4) 40% 106s, Me) 744% 10° am, 97.008. How many Na” ions ate contained in 4.62 g NasPO, How many K ions are contained in § 96 mol KPO, Fing the number of moles of the indicated species in (a) 084 g of BO, (b) 296 mg of Na,B0. (€) 875 gof Mn,0, (d) 674 mg of CaCO, 34. Find the number of millimoles ofthe indicated species (a) 64 meof P.O, (b) 1292 g of CO, (©) 30.0 g of NaHCO, (d) 764 mg of MgNH,PO, Find the number of millimoles of solute in (a) 2.001. of 27% x 10 M KMa0,. (b) 750 mL. of 0.0416 M KSCN, (©) 250 ml. of solution that contains 4.20 ppm of 10H,0. (a) 350101 0276M KCL Find the number of millimoles of solute in (a) 175 ml of 0320 MHCIO, (b) 150 Lof 80S * 10 M K.C10, (¢) $01 L of an aqueous solution that contains 6.75 ppm of AgNO, (a) $51 ml of 0.0200 M KOH. ‘What is the mass in milligrams of (a) 0.666 mol of HNO,? (b) 300 mmol of MgO” (©) 19.0 mol of [Link],? (d) 5.32 mol of (NH4):Ce(NO3)(548.23 g/moty? What isthe mass in grams of (a) 621 mol of KBr? (b) 10.2 mmol of PbO? (6) 492 mol of MgSO,? (d) 12.8 mmol of Fe(NH.):(S0.):: 64,0? 3410, 32. Important Ce smical Concepts ms of solute in What is the mass in milligra *1a)__ 26.0 mL of 0.150 M suctose (342 g/mol) seh) 292 Lof S23 = 109M HO: (€} 737 mL of a solution that contains 6 35 pp PH(NOs):” (4) 6.75 ml of 0.0619 M KNO3? SALA, What isthe mass in grams of solute in *ta) 450 ml. of 0.164 M HO,” 33. 0b) 270 mL of 875 % 10 * M benzoic acid 12> g/mol)” (©) 3501 of solution that contains 21.7 ppm of sacl (@) 21.7 ml of 0.0125 M KBrO,? SMS. Calculate the p-value for cach of the indicated sss the following (a) Na*. Cl, and OH in a solution that is 1236 'M in NaCl and 0.0503 M in NaOH. (by) Ba?*, Mn?*, and C1~ im a solution that \s 462 10° M in BaQ and 1.78 M im MnCl. te) N°. C1, and Za in a solution that s 0 500M in HCL and 0.101 M in ZnCl, (@)Cu'*, Za?*, and NO} in a solution thats 3.56 * 10°? M in Cu(NO4), and 0.104 Min Za(N0,)- 0) K°. OW and Fe(CN)> in solution that 8379 * 107 M in K Fe( 4.12" 10 Mio KOH. (CN), and wo HY, Ba’, and ClO; An & solution that is 362% Heat BMC1Ode and 6.75.10 * Mi Hao,. Calculate the molar H, Yion that has a pH of 1) 921) asy 045) tae MO 732) gg “® ~on ote, + Calelat the p-funetions fer gach ion in asl “a) 0.0100 Min (©) 0.0100 M in MO 35% 10M 0.030 Min six 10 Bac, ) 48% 19 ae 0° ion concentration of ssa an, re in Ba(oH), (Cl and 0,020 M in NaC Min Cact, and 3.6 x 10” M'* sit in Zao.) ana 56 7 10” ‘M Cd(NO,),. 38. Convert . one, flowing». tupetions to mola nee Oo mn ke = 025 ne, Bir = 034 3 a. 1235 to Anos pNO, = 7.77 PMo = 00m (Mey 130#349. 320. B21. 3.22. “03, 3D Sea water contains an average of 1.08 X 10! ppm of [Na* and 270 ppm SO} Calculate {@) the molar concentrations of Na‘ and SO}~ given thatthe average density of sea water is 1.02 g/m. (b) the pNa and pSO, for sea water “Average human blood serum contains 18 mg of K* and 365 mg of CI- per 100 ml. Calculate (a) the molar concentration foreach of these species; use 1.00 g/mL for the density of serum. (b) pK and pCl for human serum. {A solution was prepared by dissolving 6.34 g of KCI MgCl, 6H,0 (277.85 g/mol) in sufficient water 10 give 2,000 L, Caleulate (a) the molar analytical concentration of KCI [MgCl inthis solution. (b) the molar concentration of Mg" (©) the molar concentration of CI~ (@) the weight/volume percentage of KCI- MgCl 6,0. the number of millimoles of CI~ in 25.0 mL of this solution ppm K*. (@) _pMg for the solution. (h)_pCi for the solution. ‘A solution was prepared by dissolving 414 mg of K,Fe(CN), (329 g/mol) insufficient water to give 750 sof solution. Calculate (a) the molar analytical concentration of K,Fe(CN), the molar concentration of K’*. the molar concentration of Fe(CN)S~ the weight/volume percentage of KsFe(CN)s. the number of millimoles of K* in 50.0 mL. of this solution. om Fe(CN)}- (2) pK forthe solution (h)_pFe(CN)qfor the solution. A 6.42% (w/w) Fe(NO,), (241.81 g/mol) solution has a density of 1.059 gimL. Calculate (a) the molar analytical concentration of Fe(NOs), inthis solution. the molar NO} concentration of the solution. the mass in grams of Fe(NO,); in each liter of this solution. A 15.0% (w/w) NiCl, (129.61 g/mol) solution has a density of 1.149 g/mL. Calculate (4) the molar concentration of NiCI; in this solution, (b) the molar C1~ concentration of the solution. (©) the grams of NiC1, contained in each liter of this, solution, pope te preparation of (8) $00 mL of 4.75% (w/v) aqueous glycerol batrenbls dis creas © © (b) © @ © © (b) © 7 ‘Questions and Problems 3-26. 93.27. 3:28. 93.29. 3:30. 331. 3-32, 93.33. (b) 500 g of 4.75% (w/w) aqueous efhano (0) 500 mL of 4.75% (v/v) aqueous ethan! Deseribe the preparation of (a) 250 Lof 18.0% (w/v) aqucous glycerol (CHO, 92-1 g/mol. (b) 230 kg of 18.0% (wi) aqueous glycerol (©) 2.50 L of 18.0% (v/v) aqueous glycerol Describe the preparation of 750 ml-of 6.00 M HPO. from the commercial reagent that is 85% HPO. (#/W) and has a specific gravity of 1.69. Describe the preparation of 900 ml. of 3.00 MH from the commercial reagent that is 69% HNO, (w/w) and has a specific gravity of 1.42 Describe the preparation of (@) 500 mL of 0.0650 M AgNO, from the solid reagent 1.00 L of 0.285 MHC, starting with & 6.00 M solution ofthe reagent. {400 mL ofa solution that is 0.0825 M in K~, starting with solid K,Fe(CN). £600 mL of 3.00% (w/v) aqueous BaCl; from a 0.400 M BaCl, solution. 2.00 L of 0.120 M HCI, irom the commercial reagent (60% HCIO, (w/w), sp gr 1.60). (6) 900 Lof a solution that is 60.0 ppm in Na*, starting with solid Na;SO, Describe the preparation of (@) 5.00 L of 0.0500 M KMnO, from the solid reagent. 4.00 L of 0.250 M HCI0,, starting with an 8.00 M solution ofthe reagent 400 mL ofa solution that is 0.0250 M in T°, starting with Mgl 200 ml. of 1,00% (w/v) aqueous CuSO,, froma (0.365 M CuSO, solution. (© 1.50 L of 0.215 M NaOH from the concentrated commercial reagent [50% NaOH (w/w). sp gr 1525} 1.50 L of a solution that is 12.0 ppm in K, start ing with solid K,Fe(CN), What mass of solid La(10;) (663.6 g/mol) is formed ‘when 50.0 mL of 0.250 M La is mixed with 75.0 mL of 0,302 M105? ‘What mass of solid PbCl, (278.10 g/mol) is formed when 200 ml. of 0.125 M Pb?* is mixed with 400 mL of 0.175 MCI? Exactly 0.1120 g of pure Na,CO, was dissolved in 100.0 mL of 0.0497 M HCO, (a) What mass in grams of CO; was evolved? (b) What was the molarity ofthe excess reactant (HCL or Na,CO,)? Exactly 50,00 mL of a 0.4230 M solution of Na,PO, ‘was mixed with 100.00 mL-of 0.5151 M HgNO, (a) What mass of solid HpPO, was formed? NOs () o @ © (b) © @ ©Chapter 3 pt Chemin Cons i ¥ | fone a 200.0 mL of @ solu (b) Whats the molarity ofthe unreacted species to precipitate all the =e (Na,PO, or HgNO;) after the reaction was, eet & 7 Exactly 750.0 mL of a solution that contained 4s) 338, Tei] OD lr 088M mtn oa60 ‘ppm of Ba(NOs); was mixed with 200.0 mi. ‘was treated with 150.0 mL of 03912 M HCIO, and ‘of a solution that was 0.03090 M in Al,(SO,), ‘boiled to remove the SO, formed. é (a) What mass of solid BaSO, was formed? h tb) was the molarity of the unreacted ape, NO):I? ;