Calculations Used in Analytical\€hemistry, Tre International Sytem of Units (Systeme Internationa SI) fs based on the seven base units shown here and defined in Table 2-L tis the modern version of the merc stem. Since the meter (mn) was rdetined in ters ofthe speed of light in 1960, ony the ilogram (kg) was defined as an aifact (mass ofa Hatinur-risium ind stored ina French vault. Several ofthe I base units, ‘hung the agra, wore etine In 2019 accuse i this chapter, Tho outer circle shows the SI base units (mol = mole, ed = candela, kg = blogram, m= meter, s = second, A = ampero, K = Kelvin). The inner circle shows the base constants on which the units are dependent (1 = Avogadro's constant, Ky = luminous eficcy, hm Planck’ cnstant, = spead of light, Av = transition frequency of s-133 atom, e = elactrc charge, = Boltzmann constant) [ists oral mates ast samp esas of quanta analysis. We frst present the SI system of units andthe distinction between mass and weight. We then discuss the mole, a measure ofthe amount ofa chemical substance, Next, we consider the various ways that concentrations of solutions are exprassed Finally, we treat chemical stoichiometry. You may have studied much of the materia in this chapter in your general chemistry courses. Pee eos race urement 2B-1 SI Units Scientists throughout the world have adopeed a standardized system of units known as the International System of Units (SI). This system is based on the se fundamental base units shown in Table 2-1, Numerous other useful units, such as vols heetz, coulombs, and joules, are desived from these base units. In 2019, four of the seven SI base units, the kilogram, the ampere, the kelvin, and the mole, were redefined by setting exact values for Planck’ constant, 4, the elementary clectric charge, e, Bolezmann’s constant, & and Avogado’s constant, N, respectively. The correspondence between the units and the constants used to define chem is shown by the inner and outer rings of the pie chart, The new definitions were intended to improve the SI system without significantly changing the values of any of the units Unchanged numerical values considered constants of nature are che speed of light. S's the inital for the French *Systime International Unites” The dagirom unit Aina non-Sl uni of engi dat le widely wed o expres the mepliagh of ey dette ch BXrys (QA =O am = 10. ‘Ths pica X-adaton les inthe range of. 0 10.8.36 CHAPTER2 Foran aan aa Btinum-idu snc hoa ® Inosatorin Sova, Fence Unio Bam sea te, nese tedenton ofthe lesa defines tin ferns the equ asst ol the (ar Uh of a oto, gen fs enact ne an Paes satan came me Sa frat, te poo of ght sh tha frequency he hypertin arson of the Ca ater ware defied ea enact ‘tutes, aad toa stadia denon he gran intra of be an Seat" Uhia hose chanoe satay he {oundatno Stunts In nprecates {cin hoy ates sala a have Fitainiuence on paces anata Calealations Used in Anaytical Chemisty ‘Name Unit Abreviation! Tioga cond kevin a a>prosa| the hyperfine ransition Fequency ofa Cs-133 atom (frequency in He of spaifc Cs atomic transition), and the luminous efficacy (ratio of Luminous fax in lumens v0 power in wats) of monochromatic ren ight. “To expres small o ge messed quanti i terms ofa ew simple digit, preines ane use with these ase unis and oer derived units. As shown in Table 2-2, these preics mukiply eh nic by aious powers of 10. For example rhe wavelength of elon radiation used fr deemining sodium by ame photometry isabout 59 X 10-7 m, which can be expres moce compas 50m (nanometer) the wohime of igi inj ono a chromatographic column is ofien roughly 50 X 10° o 50 pl (nicole or che amount of memory on some computer hard disks is about 20 X 10" bytes, of 20 Gbytes (gaye analytical chemin, we oien determine the amount of hens species fom sas measrements For sich messrements, mec units of kilograms (kg) grams (g riligeams (2), oF micrograms (yg) ate used. Volumes of liquids are measured in unis of liters (Lilies (nL, microliters (WL). and sometimes nantes (a). “The ite, the St unc of volume, ia dered unit nd not an St base unit The teri define a cxatly 10° mn The alters defined 26 10° mo 1 ex’ TABLE 2-2 efx Abbreviation | Makipie Cee eee28 Some Inport Uniteaf Measurement 37 2A-2 The Distinction Between Mass and Weight Ieismportane wo undersund the ference benwcen mass and weight. Mass isan unchanging measure ofthe quantity of matter in an object. Weight isthe force of aracton between an objec and is surroundings principally Each. Because fravitational atracion varies with geographical location, the weight ofan object depends on where you weigh For eample, «crucible srg les in Denver than jn Arlanic City (both cis are at approximately the same latitude) because the anactive force between che crucible and Barth s smaller ac the higher alice of Denver. Simi, the crucible neigh more in Seale than in Panama (both ces are at sea level) because Earth is somewhat flattened atthe pols, and che force of ateacton increases measurably with latitude. The mass of the evucble, however mains constane regres of where you meas it ‘Weight and mass are related by the familar expression w= me where ais the wght of an object, mis is mass and gi the acceleration du vo poy ‘chemical analysis always bas on mas so thatthe ress wll no depend on Incl. A balance is wc to compare the mas ofan object with the mas of one ot smote standard mases. Because ¢afets both unknown and known equally the mass ofthe object is identical tothe standand mases wth which tis compared The disinetionbeeween mass and weight i ofa lot in common usage, and che process of comparing mases is wally called ueighing. In adton, the objects of now msi as well as che ess of weighing a Frequently called weight Always bear in mind, however, dhat analytical data are based on mass ater than weight “Thetefore, throughout this ext, we use mass rather than weight co describe the quantides of substances or objets. On the other hand, foe lack ofa eter word, we st sgh fortheact of determining the mas of an object. Also, we often say eh to mean the sandand mass used In weighing, 28-3 The Mole ‘Te mole abbreviated mol) isthe SI uni forthe amount of a chemical substance. Kis always associated with specific microscopic entities suchas atoms, molecules inns, elecons, other paricls, or specified groups of such paicles ae represented by chemical formula. One mole contains exactly 02214076 % 10° demenary eniie ‘Grom, molecules, ions, clectons, and soon). The fixed number 6.0221 4076 X 10" isknomn as Avogads constant. When expressed in the un mol this mb e call Avogidrt number, which is often rounded to 6.022 X 10. The molar mass ‘M ofa substance isthe massin grams of | mole of tht substance. We calle molar ‘aes by aummung the atomic masies of ll the atoms appeating ina chemi for mul, For example the molar mas of fmaldehyde CHO ie LmotC 20g, 2motHt 10g ‘mol CH.O * ok * ol CHO * ok ImdtO_ 16.05 ‘nol CHO * iat Mano = = 3000 gfmol CHO Masson an unchanging mesure of ie quiniy ofr Weight it the force of gvaonal amraction beech marr and Each, fmatong nd Abin dng the Apolo {obo mace But because fhe mass Sei tt cna ea he é a 2 ie js Ade erica secsThe numberof moles ofa species Xof molar mast Mele ven by Theta wrk out a welX aX/aalX ‘The numberof milliscles (anal is given by 9X smol k" Xamolk mal X = ekx When you make calculations ofthis kind yo should inchde ‘lluniteas we troughoxt this chapter This practe cen reveals errs in stig up quitions > Cuklatons Ved in Analy] Chenitay and ha of cose, CH 0g, Meng = SMA 4, ROE, maith Ug "INO. aol Gas” el * wel Cdii:O, ™ melt Snot 1608 , * Talay * into ~ 1 Melmal C0 “Thus | mole of formaldehyde has mass of 500 g and 1 mole of gluons has mass of 180.0. Unified Atomic Mate Unite and the Mole “The mases fr the cms liad in the able isd the ck nvr of hiss ate relaive msc feild atomic mat wi) a dais (Di). The dao it ki 1/12 the sof etl °C ator. Wik the enon of SU ba units in 2019, the dfnition ofthe don remsned these, However, the defo of ‘hemo and che ile changed in ach away harthe molar mas unto longer ceva 1 gfmal In ther wor the as grams of any substance in Toe of ha substance so Tonge eactly equal othe numberof akon nits average molsalar ras, Themolar msof compound days the mas of vogadot number of le casof that compound. Foret apleatins in atalyealcemy the changes ne so small ato fave ied or no influence om es, tenis 18 gol ator eB gol bl sat 2g of scree sige cubes 27 pot cules 24-4 The Millimole Sometimes is more convenient to make cllations with miles (mmol) rather than moles The milimol is 1/1000 af mole, and che ns ingame of miimae, the mlimolar mas (0) Hhewise 1/100 ofthe molar mas.2K Sone important Unis ofMeariement 19 28-5 Calculating the Amount of a Substance in Moles or Millimol: “Theewo examples tha fllaw dust how dhe numberof males or lines ofa species canbe determined fom is mas in grams or fot the mas ofa checlly lated species, Find the umber of moles and mlimoles of benzoic acd that are contained a 2.00 g ofthe pure seid 3 g/mol) ‘Solution Ee we HB wo eepreent henaead,wecan wr that 1 moe of HB har ast of 1221 g Thendore, * 1 el HB D2. gine = 010164 mol He amount He ge ~ 2.00 g HE © To cuain dhe nuber of iio die by the millimolar mas (0.1221 gma ha, ml He aunt He = 200 gts x EOL BE = 16. mol HB ta ge ‘What the maasin grams of Nat (269 g/ml) ins. g of Na,SO, (42.0 g/naT? ‘Sohition The chemical formulaindics tha 1 mole of NSO, contains 2 moks of Na chars . yc 2m Net cunt Na mye = NOG SEN Te the numker of aks of NaS, proce asin Example 2: Tol NaS 89 pn Fr ET ‘Combining sis cqunion wich he ia neo Ln aSO% 2d Nat Hg, * mL, “To gbrain the mas of sodium jn 250 g of NaS mukiply he nuber of moks of Ne" by the mole muss of Na" 0622.99 And, oun Na DOgNESO; x 2299 @Ns" =r mas Nat = axl Not Sitesi te pious opin gs he massin grams of Nat Lal NeSO , 2aolNr THO ges, amb NeESO, amd sme Nat 0g NAST, x 10g Gi ere ca ey ‘alone andin seace aravaCalesatone Used in Assy Chemisty ‘The Factor Label Approach to Example 2-2 Se malcna aad niacin Ld vou whe de oa od pelo thar sin the denominator of ach atcenting term eine the un the a ‘ert ofthe preceding oe ul the unite of the answer an obi. Ths method Ine ben eer the ataelabe method, dimensional analy, ede picket ett Fates ail oberg oa ‘he es en ae g NSO, Thu, can write rl NaS, 20 gas; 25.0 pdias9O7 x it cline ks of N50) mW, _2mol Nat 250 Nasr x GENE a andthe ciminae moe of Na The eu is jc mob NeSO} 2 male 22.09 Na 250 gNeBOL 300 ge * el NaS, a = 810 Ne] (Over thecoune ohisory, measuroment and their cortsponding uni were invented st the loa vel, By mecesty of priitvecorwumniction wed local echnlony, standards were neatly nonexistent, and conversions among the many systems wee ic The sul was many huis of distinct ways of expresing conceatasions of saludos. Fortunately fru, da advent of rapid ommunicatons echoolgy and the development of int te have fore globalization of measuement nce tnd, along with the definition of glabal measurement sandants. No fld bas enjoyed enore benefit in thi toga than chemistry in general and analyte chemistry in pardcuat. Even 1, weute + numberof methods for exprening concentration, 28-1 Concentration of Solutions There are four fundamental ways of expressing slution concentration: molar concentetion, percent concentration, soution-ilyne lime rato and p-intons, Molar Concentration The molar concentration ¢, of a olucion af solute apecis Xs the number of| sols ofthat species hat scons in 1L ofthe solution (no 1 Left sen Tn terms ofthe numberof moles of salu, and the vlume, Vf slain, wt a es) ‘Tea a pol eae mai an EBay! Ch 68 40) 97 DON MIO28 Sohtion and Their Coneentatons 82 “The unit of molar concentzton is maar syabelzed by M, whic has dhe dimen sions of mol/L, ox mal |. Molar cuncentatio Isao the number of milimaes of sslts pe mille of lution. mal sna VNC tint BL nl tt = 1 eee ee eras contains 2.2 gaf GH,OH (4.07 g/mal)n 2501 of salution Soliton To caelate molar onceneton, we mu find both the amount of cthanl and the volume ofthe olan, The volume gent 350, oallwensed w dois ocomert thems of ethanol the conepending amount of alia nk Lol HOH. amour C1KOH = niga = 230 gO = 004992 mal CH0H “Toobin tbe concent gop Ave he tin ithe ii Ta saopeanortc 18! GHOH _ OBO Tor gGotKOrT = 00143 mol CHOH/L = 0.0143 There are evo ways of expressing maar concentation: malar analytical concen tration and molar equlibrtes concentration, The datinction berween thee wo fexpessons ic in whether che salute undergoes chemical change inthe solution proces. Molar Analytical Concentration The molar analyeical concenteation, of for che sake of brevity, just analytical concentration, ofa solution goes the tal number of moles ofa solace in IL of the solution or the tor numberof milimoes in 1 mL). In other word, the molar analytical concentration specifies a recipe by which the solution can be prepared segatdee of what eight happen tothe solute during the solution proces. Nove latin Example 23, she molar eoncenttatio that we calculated is also the molar analytial eoncenzaton coy = 00143 M beans she solate chanel molecules, tre unchanged following de slurion proces Inanother examples aul ec solution shat hasan analytical concentration of ‘nig, = 10 Mean be prepared by diwolving L0 me, 98, of H,SO, in water ata duting the acd oexaeay 1.0L, There ae important diferences beewoen the sthanol and nfs aid example, ‘Molar amyl concentation ‘Seal mune of moles oles, eee Gerace fecal ete ae eel ae ree te prepaa CHAPTER? a se therolar conenaron oft eee ieee In your cud of chemists youl bad hat temainlouy Sonutanty evolves ares tine cr undertiog of te processes that we tcl and Calbeyor to desbe then now ecurately Molarity, whichis synonym or mole Gresotsion inex eon of aterm thats reply gotog xtelfchian, Although you, nay finda few occurences of ‘polarity sea synonym female ‘concentration in his textbook, ‘peeved whenever posal “he IUPAC recommend the genarl term concentration {oespres the companion of asoltion vith respect its ‘els with or uber ‘ene coneantation alae ‘oneentration and number ‘encenttation Molar ‘oncentation, rhe eral ‘oncentation, and molar libri centration wall ‘hour concentrations by thie Seiniton, In this example the molar uljealconeonrotanct 1480, iscver by Sgn," [502°] + [850¢] acs SOF” and HSOT ae Sony wosulatecontining Species eslaion The ilar alien coneweetine eons ae [S02"]and fas0;} > > > Caletone Used in Anal Chomisey ‘Molar Equilibrium Concentration ‘The molar equilibrium conceatration, o just equlibeium concentration, sfes to the molar concentration of a particular pecie in x solution at equilibrium, To specify the molarequiibrium concentration species, ts nace ro know how the solute behaves when itis dsilve in a solvent. For example the molar equlib- ‘Hum concentztion of H:SO, ina solution witha molae analytical concentration ‘so, ~ LO M actualy 0.0 M because che sulfuric acid is completly dsoviated into 4 minute of H”, HSO,”, SO," lons. There ae esentlly no H;S0, mole- cues in this sluion. The equlibium concentrations of she ions ae 1.01, 0.99, and 001 M, especie. Equilibdum molar concencration ate wally symbole by placing square brace «te atound the chemical formula forthe species. So, For the solution of H,SO, wth ‘an analytical concentaton of 9,0, = LOM, write (M80, (807) 00M iw) 99M [S02] oom o1M Calculate the analtial and equlvium molar concentrations ofthe solute species in an aqueous solivion that comtaine 205 mg of trchlerescetic cid, C1CCOOH (163-4 g/mol) in 10.0 ml (the acd is 73% ionized in water) ‘alution Asin Example 23, we clcuite the nurber of moles of C,CCOOH, which we designate as HA, and divide by the volume ofthe sltion, 10.0 ma, oe 0.0100 L. ‘Then LgHA Lol HA 0 wgHA * Tah.a gH L744 x 10% anol HA, amount HA ~ mg, = 285 mg HA x “Theta abel inating han 1.744 X 107% mol HA 1000 a _ 9 mo HA me Tho mt a BAG, In chs sahtion, 79% ofthe HA dsc, giving Hand A HAS Ht EAT “The equlvium concetnion oF HA is then 27% of Thus [114] = gun * (100 ~ 73)/100-= 0.174 « 0.27 = 0.047 wal = oo “The cqulivium concemation of A~Is equal o 73% ofthe andy concentration PHA a Pimol A> 1 joo poten * 01 (comin)28 Solutio and Tiss Cancenations 29 Beste 1 moe of sored fr ech ne aF A", we cn a ws [w*]=[a"]=o.27a1 ad [HA] + [A-) = 0047 + 0127 = 074M Describe the preparation of 2.00 L of @108 M BaCl. from BaCl,+2H,0 (ua g/mol. ‘Sohition To determine the mas of slue tobe dinar an dtd to 2.0L, note that 1 nde the dds yields Tale of BaCl in aon, Terre, o roduc this tela, we need 0.108 mol Bac 2440 200 ¢ MOS met RAC EO 16 al Bac“ 28,0 “The mas of BAC, 28,0 then 0 0216 mal BNC PAEO = 528g BC 2H0 Disoie 52.8 g of Bal 2H, On wae and dite 2.00 Describe the preparation of 500 mL of 0.0740 M CI” solution from solid BsCI, a0 au gfe. ‘Sohtion 000 EE yyy ye BOLE a0 rss BuCl,- 2440 2 flees 4 243 g ACh 2140 pale aT 452.9 4C-244,0 Disolve 452g of BeCl +210 in wae and lute 00 30 Lor 500 mt Persent Concentration ‘We sometimes expres concentrations in vem of percene (parts per hundeed) Unforenaiey this practice can bea source of ambigicy beause percent composi= tion of slution can be expressed in sever way. Thee common matheds ae Nolet ode fetes a ChCCOON Heh sora ‘The number afmcleso the spaces Ain esolaton of Als =o) no.molA = nq = 04% Ya pal realy veboreVieth volume othe {ohtion miter.24 CHAPTER? ight percents more prope balled maz: preont od bbrevsted n/m The term weight percent isso widely teria hp checteal ening Tames that wel ust throughout this text In TUPAC teminolapy weight percents Ia UPAC rly lane ine, teers 2 Ie IUBRC ais prbilenpeepesiion > tps pesto Abuse weblog pera to remeber Feral secu lain whose ‘bres er proximately 200 gly ppm 100 gf Thitig ___tsscoie(s) rm” Faas elution (Q) x otppm (__pisssote (oe) Sm * Salar latin (°F ee) (Ceations Used in Anagicl Chemisty sgh sole weigh pen (om) eh lunon vane eee) = SS ap vwihotolne pen) = Te 096 ame voltion a [Ne thatthe denominator in each ofthese expresionsis the mt or woke of whi rather than mau or volume fslvent. Note leo that che Bis two expresions donot pen onthe units used fr weight (mass) or volume as long asthe sume unis are ‘wed in the numerator and the denominator. ln the thd expression, units must be dined because dhe numero and denominator have deen units that do not cance (OF che thse exprestons, only weight percent us the advantage of bing temperate independent ‘Weight percent is fen wet expres the concentration of commer aqueous agents, For example sc acid fold a8 a 70% (of) solution, meaning thatthe agen contains 70g of HNO per 100g of slain (se Example 2-10) ‘Volume percent is commonly used to spcify the concentration of soluion eepaed by dling a pure liquid compound with anther liquid. For example, 45% (v¥) aqueous solution of methanol way describes solution prepared by ding 5.0 mL of pare methanol wit enough water give 100 mL. ‘Weight or volume percent is often sed to indicate the composition of dure aqueous solutions of solid seaents. For example, 59% (wt) aqueous silver nitrate fen refers solution prepared by dsolsing 5g overnite in cent water {0 give 100ml. of wltion, To avoid uncertain, always spclyexplicidy the type of percent composition ling discused. this infcmation sensing the investigator must decide incite sich of the seve yp iso be used, The potential ror ring, fom a wrong, hice isconsderable. For example, coramercal 50% (wh) sium hydoside con- ‘sas 76 g NCOH pe lite, which conesponds to 76.3% (wh) sodium ydroxie. Pastsper Million and Parts per Billion For very due soluions, parts per mllion (ppm) is a convenient way 0 express nas of sole FS naw there fps te cancentaion in pars pr million, The units of masa the surner- atocand denominatormust arc so that thy ancl For xen more dilute solutions, 10? pp rather than 10° ppm is used in the previous equation to give theres in parts per billion (pp). The tem parts per thousand (pp) is ao used, expecially in oceanography. What is the molar concentration of K* in a solution that contains 63.3 ppm_ EK Fo(CN)aGsB3gh00)? Aoontnuel)2B Sohilonsand Thole Conconvations 25 Sohition Analysis ofthe units shows that Because thesltion'sso dl iis esonableso assume that ts deny. 00 gn Therefore, acoding 0 Equation 2.2, 63.3 ppmKyFaCNe~ 63 meKFeCNYAL 2m, eet. ramal KRdCNs_ B3mKEMENE 1 pkiFefONT. L 1000 ig FEET, «al eee ees 1a 1 ‘concentration expressed in eee! i oie 2x 10" 1.922 107 GRANT, waneaesnpe inequivalent tata mg/L itivepreseding/s.emst toulpy the ratioby 10pm, For parts per blon ppb tan stg] inane soliton (9) X10? ppb Solution-Diluent Volume Ratios The composcion ofa dite slution i sometimes specie in cems of the volume of more concentrated solution and the volume of solvent used indian it. The volume of the formers spaated fom that ofthe later bya coon, Thus a 4 HCL ass oh a) tle coe or aes ef fre vekmecfemceemed yiehlor | eg Seat tac Ths meso rotons gly ambguosin hate camennion yea often solution sma alvssobvios Macoverundesne icunstances Tor mascomentinn nm {iment dt one vine vith hee volumes Beau of sch unceainiesyou ‘hod ising lone p-Functions Sdesdes legends ope dacoteenenlonstcppeleorermestinp leon, So ain The pac tanga opton be 10) of cone teen of pen Thu fre rer pX= ~leg(X] han As shown by the following example, paalus ofc the advantage ofllowing on= cenmaionsthat vary vee 10 or more oderof magnitude robe exresedintermsof iePHewhichsthe negative legatdn of (H*] We dice sul pose numbers aisee ens inaqueos soltion athe sematverepresenttin HO" In Senion 782 pA = log “To obuan Na, write pNaA= ~logiNE"T = “log (2.00 % 107 og (54 104) = 3.27 log (2.00 % 1079) = 299 (comme)omar mala HCL Hytonen ‘hich consssof HO" are Crs. Demy een thera os Geese eee nk deny posed nis of gl orakerscy ga ‘Specie gas ithe ao oe Seivofatainene eae ‘sal lume of wae, (iene Used a Anahienl hamiy “Te etal CI concent sgn by the tn oF the consents of the ewe sohes [or] = 200% 1079 M4 54 10 = 200 x 107M +054 % 107? M = 2543 1072 PCL = “logl 7] = “hg 2.54 10°? = 2595 [Note that in Example 2-8, and inthe one that follows, the sults ae ounded scconding othe rales ited on page 73, Seton 4D, Calculate the molar concentrationof Ag ‘Solution solution thathasa pAgof 6.72, loglAg") = 6372 6372 246 1077 = 425 107M 2B-2 Density and Specific Gravity of Solutions Density and sei nvity ate ated rms ofen found in the analytical Hear. ‘The density ofa substance sis mass por uit volime, and it specific gravity the rao oe mats tothe mats of un equal volume of water a 4°C, Dens has unite cf lograms pr lero grams pr illite n the metic tem. Specie praviry it dimensionless and so is nor ed to any particular system of unt. For this reason, specific gravity is widely used in desebing items of commerce (Se Figuro 2-1) Since the dens of wate i approximacey 1.00 gl. and since we use she meee ‘pate thrnaghout this ext, we ue deny and specie gave interchangeably, The ‘Pecfc grits of some concentrated acide and bss are ven in Table 2-3. Caleultethe molar concentration of HINO, (63.0 q/mol ina solution that has specific gravity of142 and is 705% HNO, (w/v). ‘Solation Fay lela the mas ofa per er ofeonecnetd soon gHINO, 142 igi 10" gangs TS gHNO, _ 1001 HNO, regent "reagent reagent 100 geet Lreagent Then, 1001 gHNO5 I mal HNO, 9080" “Tregenr GO gHNG; Leeper38 Solionsand Their Concentations 27 wet ae Lglpre temo isiies tnichremer cic sertememn ee Coeereen soir) Tos 0 19) ts 1a ‘s i 1a solution that has a specific gravity of 128 and is 37 (w/w) HCl (365 g/m. ‘Sohution Proceeding in Example 2-10, Girt escalate the molar concentration of the omcentned reagent. Then calculate the muinber of mole of id worded for the fentid)28 CHAPTER Equation 24cun be wood with sl mol/l oral end ola Thos role, Bat Tent Ta Lana x (Cuntions Used in Anaya Chemisty Sed ston ally, hide the second Ge hy the Gi wo bain the vole of Coneentrd aid ee Tha to obtain the conantraton ofthe reagent ite L110 pet 7 HET 1 mal HCL “Te numberof makes Clete given by , 160 mal HCI mal HCL = 10 tx GE 5 Sma! 659 ol HC Fly bie tn oan gents it ne" ~ 20M 1 Lean Tao mol+4Cl “Tarts dite 50 ofthe concerted reagent 600 vel cone reagent = A600 moLHICT x = 00500 0" 500 a, ‘The solution to Example2-11 ished on the fllowing sf elation, which ve use often: Van % fant = Vat * 6 9 ‘whesthe owotemsn the lef ae the volume and mar concentration ofa cancea- tated slution thats being wed to prepare aditaed scuron having the volume and ‘onecaration given bythe comesponding terms on the ight. This equation is based fn the fc tha the numberof moles of solute inthe lied solution mus al the faumber of maesin the concentrated reagent, Note thatthe volumes can be nal ters or itera longa the sae unlts ate sed fr bath sutons ‘The stoichiometry ofa easton Siete erate ‘Surber after of ractints Sn product as epresented by « elec chested ogi ‘Stolchiometry the quaniutiverealonsip among the amounts of reacting chert ical species. This scion providesa brie eview of sochiomerry and its applications to chemical aesatons 2C-1 Empirical Formulas and Molecular Formulas ‘An erpiial formu gives the simplest whole number rato of atom in a chemi- ‘lei ones, telecon oes ipo dh te feb fold Ta eis beni np ha sal Pl bt ferent mokcular Formulas, For example, CH,O ie both the empiri andthe mo- scl formula fr formaldehyde; ii als che empirical Forma for sich diverse subuancesasaceti sid, CsH, Openly, C,H,O,:and glucose, CH, swells more chan 50 other substances containing 6 oF lewer carbon atems. We may calculate the empirical formula of a compound from its percent compost tion, To determine the molecular formula, we must know the molar mas of the compound.Die by———Mutiyby —Netupy y A structural formula provides additional infomation. For example, ethanol and ioe ether share the same molecular formula CHO, but they ate chemiclly quite diferent. Thee seuctatal formulas, HOH and CH,OCH,, reveal seue- ‘ural differences berween thee compoundsthatare not shown in ther commen mo- deca formula 2C-2 Stoichiometric Calculations Abslanced chemical equation gves the combining rates sochiometey—n units of moler—afeacting mbsances and thee produ. Therefore, the equation _Nallag) + PL{NOs)lag)—> PhI() + INNO a9) indicates that 2 moles of aqucousvodium jodie combine with 1 mole of aqueous lead nitrate to produce 1 mole of li ea iodide and 2 moles of aqueous sadam [Example 2-12 demonstrates how the mae in grams of eacant and products ina chemical ection are related. Asshowa in Figure 2-2. calalaton ofthis ype isa ducetep proces of (1) tarsorming the hoowe mas ofa substance tocar responding numberof mols, (2) mulkipying the mumber of moles by a factor that, account forthe sschiometry, and (3) convening che numberof mols back to dhe reise uit called fori che ane. of AgNO, (1599 g/l is nzeded to ene (Gobo gin 6 AaCO (5) Wht mae of B00, 75 al “Solition (8 NssCOsag) + 24NOMag) > ACD) + 2NANOSaq) ‘Sep. amoune N00, = Ay 1 mol NOs 30 Ee 06 pase; 1102198 mol NasCO, (oi Ser qurpc wu ataangoute dpc Acree wemofchned ampere tite onmacanygeetn ow sa pon pare ag) = ah = PL) 20 Chemical Stchomety 29 FIGURE 2-2 Flow dae atin schon deters he teens recnter posts gen the Stes, singe ras. Gomes uaor reason tanec hat cones wh Iriel poset ns. 9 Pay, te mash treat the Cent physic ae of stances sppeing tuations isinceatedy the Jere), (ee rhich selerto genus iu sold, sid aqueous wolaion sate, epectvalyfron retiods 106000 A Brosnan ventana resognnsrecaech Spectometty. Cberical and Engineer (Clann Used in Abril Chemin ‘Step 2. The balanced oqustion reve hat mol AgNOs Teel ie005 sunt AGNO) = agxo, = 002198 min} % = 004396 mal AgNO, Ia thinineance, the soichiometc Fazer in(2 mol ANO,V(U mal N Sep £03. AgNO, = 104396 wot AgNO; x PP EMENOS «7 47 gyno, 7 ; ARNO, (amount AgsCO, = stount NasOO, = 002198 mal 252 §AGCOs pelt; ‘What mass of Ag;CO, (2757 g/ml) is formed when 250 ml of 0.200 M AgNO, e mised with 5&0 ml. of 10800 M Ns,CO,? mass AgsCD, = 002198 snl Ags O05 X = 65 gAg:CD Soliton Mixing thew tw saltions wil rele fn one (and only one) oF sree posible (@) Ancxess of NO, remains alter the reactions comple (@) Am exes of NCO, remain afr the eatin is compe (© Thete sn excess of ether reagent (tha she numberof mole of NesCO4 is cacy equal owe the numberof mols of AgNO). Aas tp, tals which of thet suations appli clang the amounts of rexctams(n moles) aval Before the solons ne mix ‘Tein amit ate amount AgNO} = ngs 2200 me ABNOS = 500 x 10°? mal AGNO, Taghio; seco “ao apts x LMSC: aunt NCD, = myc, = 900 mL NOR SS i mal NasCOs LNs€0; Because cach CO ion ets with wo Ag fons, 2 4.00% 107? = ROD X 107 tol AgNO rested to ect withthe Ns,CD, Sine we have inafcient AgNO, ‘ration (b) preva and the number oF moles of AGO, rode wl elimi by the snout of AgNO, anil, Tha, 00 % 107ml NaJ0O5 a yc LabteseO§ 2757 gARCO, ins AC ~ 5.00 10 AO SET = 0689 pagCO,‘What isthe molar analytical concentration of Ne,CO, nthe ston pro duced when 25.0 ml of 0200 M AgNO, is mixed with 50.0 of 10800 M Nec0,? Soliton In the previous example the formation of 5.00 X 10" wal of AgNO, reas 250 10 lf NCO Thema ste ofa NCOs mee sien by a. o Ll NCOs ‘y= 401% 10% mal NCOs 500% 10% mal x = 150% 107 mol NCO, By definition, dhe molar concession ithe numberof males of NCO gt. These 150 x 107 mel NOs 000m Cs an = 00200 M Nss00, “Many chemical calculations canbe performed in speadsnet applications such as Excel. A few examples are given hee, but a detaled introduction to Excel and its Fundamentals ar found in the companion text Appliesion of Micro? Ese in Anabical Chemis, Sth ed, Cengage Learning, 2022. Those who purchase the ‘ure text hae fl aces otis companion txt. Example 2-12 isthe fist example ete There te many ways tose up Face «9 othe rave simple mkipications and divisions need in Example 2-12. How ever, consistent approach is wie. One method thats helpful sto separate the known quantities, th calealatons, andthe documentation. In part (a ofthe exe ple, the mass of NiCO,, the molae mass of NigCO,, the mae mass of AgNOs, andthe stoichiometry are known quant, In part (b), dhe molar mass of AgxCOs and the stoichiometry are known, The aleultins are shown in Figure 22. Since this calculation i reatively straightforward, the equations can be developed caily from a sichiometric oa fctolbel approach The rele ae shone in Figure 2:3, along with the documentation, (One consistent way to document that avoids reryping the formulas entered in cells BL, B15, BIG, B19, and B20 iso copy them into the documentation cell “Thsapproach aide making eor by retyping the formas, We sow this method ‘with che documentation fr cll B14. Ifyou just copy the contents of ell B14, the Formula is copied, bu the cell references in the formula change To avoid this, click fom call B14, highlight the tex in the formula bar, copy ies contents (CteL-Cor click the copy ion) and pres the Bape he co remove the highlight from the coments of ell B14, The coped tet, = BA/BS, itil onthe cipbaued, Now select el 23, poston the cursor inthe formula bar. type cll B14, and pate (Ct or elick the pst icon). This copies che formal a3 text sng cll A23. The oer formulas «an be copied in the same way. While tis easy 0 retype these simple equations, for more complex calculations this approach ves tie and ids many pose eto Example 2-153 more complex example from gravimetric analy,ge CHAPTER? FIGURE 2-3 Spretsoet etn of ha mass afreget neotedans the grout tt rot foros n to raion t tote sputn rau elations Usdin Analy Chemisty 4 Mess RINaCO, 238.0 5 Molar ies RI 1060 got 6 |stienonetne Rito 7 7a Ago 8 Motor Mess R2—1889 got 9 |P 49,00, oo 21517 gmat 1" “12 Calculations 13) @ 14 Arount Rt 002180 mat 15|AmountR2 needed 0.0490 mh 18 Mess Reeves 147g 7 8 ® 19 Arount P formed 00290 mt 20 Mass P formed 108 0 a 22 Documentation 2 ca -04 24 Cal B15-81e"80 25 cot Bi6-B15'88 25, cat pis.ae 27 Cot 820-8190 An ron ove i analyzed by dissolving «13924 sample in concentrated HC, ‘The resulting solution iseiuted with water, and the iron(II) i precipitated asthe hydrous orde Fe,0,-xH,0 by the addtion of NH, After filtration and ‘washing the residues ignited at a high emperature to give 00549 of pure Fo,0, (15969 g/mal). Calculate the Fo (55.847 g/m) inthe Solution Fin, eter the known qunttie—she mass of the simple han the mas ofthe recipe and he alr mass of Fe, O,FesOs, and FeO The amoune of FeO, found fom the mas of FeOyand the molar mas, Ail Fey FeO “The number af moles of Fe sic that of Fes0y which allows elation ofthe sss of Fe, nouns Fe, = gO; * (minal)20 Caeaatone Using Miron acl” 99 ei fae pncnnge of e aio Revi by e ep ae se zaps re % 100% You en ali ind the percentage af FeO, by noting tha 3 ml of FeO, produces 2 ma af FeO, aca othe lowing ston. 88610, 2Fe,0, + 10, “The trons nd the documentos te showin gue 2-4 4 > 1 2] a A tise | 11024 sim, 55,845) “elu, | 15990 7 lMrsoy | 1996087 * Moos | 231831 10 (Calculations: ‘re um A200, | 46.04 1 2 14 Documentation 15 Cot 811-8987-2"8564"100 16 | cet 812-Bu67°25"BONBE"100) 7 FIGURE 2-4 syrentiwetter grsimetie In his chapter, we have reviewed many of the baste chemical concepts an hls necessary for efctive study of analytical chemistry nthe reroaining chaps ofthis ook, you will build on this Firm foundation as you explore methods of chemical analy, Search to Bind a any defies ofthe Klegea a you can, Wy ate threo ey dfn! ‘mci the pltnureidn llr hat yas te standard pio 9 2019 Hoy ihe 2019 del ‘ion in improvement on this pets logan Why isthe 2019 desien a ae stable vai) Aether propored andl pie vo 2019 wad the cl ecos Mla. Dacre hs propre ‘tndard and compac tothe 2019 dfisien ofthe kop,24 CHAPTER? (alsstione Used in Arial Chemin Cees +The national Sater of Unit (1 i bused on seen fan damental ae unis tilggrn ante ne apes, coed kein and cx. «+ Revisions were made in 2019 redefine che iloam, the ampere he ma, and thelein The niece bet ee mal ih, Harden meinen ear meri subarance wl weight the re Farrar erween an objec and isnrounding. + he deo yeti noms, desos, ont, or merle) cette Arogades umber ofthe ent, + Avopudesconsan can exact number 02214076 X 108. Avogd' sumer ‘Aogadconaans por mole “Theat ofa absence the numberof ga ofthc ubnine tnt mle of tot sbetance, + Solution concentrations can be expres a molar concentrations pas pe lon chon puncibes. ar enon + Mol concntaors ct be molar abil or mab equim concentrations + Micosof Exe an clea concenations and stoichiometric quate in che teal acon, [aa Densiy, p26 Molar concentration, p. 20 Parts pee million, p24 Excel calelations, p31 Mole equilibrium concentration, Function, p25 Mass. p17 pm Speci grevity, p26 “Molar analytical concentration, Molar mass, p17 Stoichiometry, p28 pai Mole, p17 Weight,p.17 Pee role ‘lime ofan in es “oy Concentration in pats per million mus slate = BEE ppm act % Sant ™ Vas XaDefine “Q) molar mas. (6) millimole (0) millimolar mas. (8) pats per billion 2-2, Wharis the difference berween molar species concen- ceation and molar analytical conecettation? Give two examples of units derived from the funda- mental base SI unis. 2-4. Simplify ee following quantities using a unie with an appropriate pei: (@) 58 X 10" He ) 437 x 077% “931X107 mol (@) 83 x 10s, “(@) 336 X 10° am, 8, 53,000 g. “25, Why is | g no longer exactly 1 mole of unified atomic 2.6, How did che definition of the mole change with the 2019 reeinton of St base units? Find the number of Na" ions in 2.75 g of Na,PO,? Find the number of K* ions in 1.43 mol of KoHPO? Find che amount of the indicated dement (in mols} in (532g 0fB,0;. (6) 195.7 mg of Na,80, - 10H,0. (0) 496 g of MnO. (4) 333 mgof CaCOy, 2-10, Find cheamount in milimoles of the indicated species in @) 1292 gof NaHCO, (b) 57 mg of MeNH.POs (6) 850 mgof P.O, () 400 g0f CO, "2-11, Bnd the number of milimoles of shite in {@) 2.00 L of 0.0449 M KMn0, (6) 750 ml of 535 X 107° MKSCN. (6, 3.50 Lof a solution thar contains 6.23 ppm of CuSO, (4) 250 ml of 0414 mM KCL 2.12. Find the numberof rillmols of soit in @) 386 mL of 0210 M HCIO,, (6) 25.0 L of 805 x 107 M K,CxO, (© 4501 ofanaqueos sohurion that conans6.95 ppm of AgNO, (8) 537 ml. of 00200 M KOH, "2:13, Whavis che mass in milligrams of (@) 0367 mol of HNO¥ (6) 245 mmol of MgO? (9) 12.5 mol of NH,NO}? (4) 495 mol of NH)sCANOs), (548.28 g/mol? 2-14, Whar isthe massin grams of {&) 2.25 mol of KBe? (6) 15.5 mmol of PhO? (©) 5.04 mol of C2502 @) 10.9 eum of Fa NH)y(SO4)- 6H,08 2-15, Whar isthe massin milligrams of solute in a) 16.0 mL.oF 0.350 M sucrose (342 g/mol)? “b) 1.92 Lof 376 X 107M HO {€) 356 mL ofa solution char contains 2.96 ppm of PO(NOS)2 (@) 5:75 mL of 0.0819 M KNO3? 2-16, What isthe massin grams of slut in a} 250 ml of 0.264 M H,0,% "() 37.0 mLof 5.75 x 10™ Meni acid (122 geal)? (©) 2.50 ofa solution that conan 37.2 ppm of nC? (@) 11.7 mL of 0.0225 M KB:0,? 2-17. Calculate the p-alue for each of ee listed ions inthe following: (a) Na", Cand OH ina solution thai 0.0635 M in NaCl and 0.0403 M in NaOH. (0) Ba, Mn", and CI" in a solution tha 4.65 10"? Min BaCly and 2.54 Min MnCl He) HP,CI and Zi ina solution that is 0.400 M in HCl and 0,100 M in ZnCl (@) Cu", Zn°*,and NO; ina solution chatis5.78 X 107M in Cu(NO,), and 0.204 M in Za(NO,) (6) K*,OH and Fe(CN¢"inasolution hats 1.62 x 10°” Min KyFe( CN)and 512 10”” Min KOH, (9B, Ba’, and CIO M in a selon that 62.35 10™4Min BulGO,)sand 475 X 10“ Min HCIO, 2-18. Calculate the molar HO" ion concentration of asolu- tion thachas a pH of a) 3.73 () 328. He) 059. @) 11.28, 4e) 7.62. © 5.09, gh -076. te) 04. 2-19, Calculate the pfancsions for each ion in a solution thas fa) 0.0200 M in Nab. (b) 0.0300 M in Bab. Ye) 45 X 107? Min BOK), (@) 0.020 M in HCI and 0,010 M in NaCl Ye) 72 X 107M in CaCl; and 82 X 107M in B.C (28 X 107M in Zn(NO,), and 66 X 10-7M CaN),96 cHAPTER2 2-20, Conver the fllowing p-functions to molar concen- a) pH = 1.102 (©) pOH = 00087. M©) pBr= 77, (@ pCa = “0221 (@ pli= 1235, © pNO, = 1.054 “ig pMa = 0135. (h) pCl= 892. “221, Seawater contsine am average of 1.08 % 108 ppm of Na" and 270 ppm of SOJ~ Calculate {@) the mo concen of Na” and SO2™ gven tha the average dey of serwater i 1.02 gel (©) the pNaand pSO, for seawace. 2.22, Average human blood contains 300 moe of hemo- fobin( HB) per liter of plasma and 2.2 mmal per iter ‘thule blood. Clalte {@ the malar concentra in ech ofthese media (6) pin plnma in hursn sera, "223, 4 solution was prepared by disolsing 5.76 g of KCI MgCl; 620 (277,85 nol in slfcent wae cer ge 2000 L. Calculate (@) the moar anaicl concentration of KCI- MgCl inhi slion, (0) the mobs conceneaion of Mg. © the mob concentration of Cl (@) the weight/volume percentage of KCI-MgCls ait. © the numberof eillinoles of CH” in 25.0 mL. of this solon © ppmk" (© hg forthe solion, {h pClfor the solution 2.24, A solution was prepared by disolving 875 mg of K,FCN), (329.2 gil) in suicent water wo give 730 mL. Cale (2) the mab nail encanto of KjFACN) (6) themok concentration ofK” (© the molar concentration of FCN). (@) the weihuvolume percentage of K,EACN), © themumberof millimoles of Kin 50.0 mL of his solon © theconcenraion of (CN in ppm. {® pK for the sltion {h) pFe{CN forthe soit, "2.25, 45.85% (wi) RANOg) (241.86 pmol soluon bss 2 deniy of 1.059 gf. Cleat {@) the mols snap! conentration of F{NOs yin ‘his slon (0) the molar NO concentration in the slain. (© the mas in grams of Fe(NO)scontsined in each ler ofthis soon ‘kelatnns Vee in Anaptcel Chemisty 2.26, A.11.486 (fe) NCL; (129.61 g/ml) soluion has a ‘deity of 1.149 gf. Caluite (a) the molarconcentation of NiC i his soliton (b) the molar CI“ concentration of the soution. (©) the mass in grams of NiCls contained in each iter cf this olution, “227, Describe the prepaition af {@) 500 mL of 5.25% (w/v) aqueous ethanol (C.H,01, 46.1 ginod, (6) 500 gf 5.25% (vw) aqueous ethane. (©) 500 ml of 5.25% (we) aqueous echanol 2.28, Desc the preparation of| {a) 130 Lof 21.0% (w) aqueow glycerol (Hy, 32. gla) (b) 1.50.kg of 2.026 (wn) aqueous yer (©) L501 oF 21.09 (vy) aqurous glee Desctibe the preparation of $0 mi of 3.00 M HPO, fiom the commercial reagent that is 864% HPO, (w/w) and has a spe gravy of 71 Dacibe the preparation of 750 mi of 3.00 M HNOy from the commercial reagent that Is 70.5% HNO, (vd) and has a spate gravity of 142. "231, Dace the preparation of| (a) 500 mL of 0.1000 M AgNO, from the solid eng. (b) 1.001 oF0.1000 Mt HC, searing wih 3 6.00 ME sohsion ofthe regent. (6) 250 fa slain that 80.0810 Min sing with sold KFC) (4) 500 mL. of 8.009% (ws) aquenas BaCl, from a 11400 M B:Cl,soluson. (©) 200 1 of 0.120 M1 HCIO from the commercial reagent (71.0% CIO, (wn) sp gr 1671 (9) LOU of slution dat 600 pps ia Na seating with slid Na,5D,, 2.82, Deserve the prpaaton of (a) 2.50 L oF 0,0250 M KMn0, from the solid seat (6) 4.001Lof0.250M HCIO, startingvithan 8,00M solion ofthe reagent (©) 500 ml ofa solution thas 0.0200 M in I, stare ing with Mely (4) 200 mal. of 1.00% (is) aqucous CuSO, from a (1.365 M CuSO soltion © 1501 of 0.300 M NaOH fiom she concentrated commercial reagent [502% NiOH (wh), sp 1.525}. 1.50 Lofasoluion tha is 15.0 ppm in K*, star ing with sold K,Fe{CN, “233, What mass of sold L3(103) (663.6 gna) i forened when 50.0 ml of 0.250 MC Le? nixed wih 75.0 mL £0,302 M105 2.34, What mass of solid POCL, (278.10 ghmol i Formed sv 200 ml of 0.128 MU Pb is mined with 400 mL of075 Mc"? “229, ©