Stewart"s

Te-xtibook of Ac id .. IBase

,John A Kellum, MD, f:AiCP, FC:CM" IFCCIP

Professor of Critical Can~ Medicir!H;:, IDepartme!rnt of Critk:a!1 Care Mledii,c::il1!eJ Uniiv,ersity of IfrlliUslburgnl Schooll of Medicine, 1~littsoUiirgh, P'ennsylvania, USA

IPalul WG IEllbell!s,. IMID

D€lpartm~lIi'It of Anes:tlh,~siaj Ilnltelnlsiv€l Calm and Pailnl Mana,gl~m€lnt! St. Arllto nli us Hllospitall f INI ileuweg eli n,'lhI,e N,etlhl,erla nds

IP,ete:11i' A SteW2IIIi1:.. Ph D' t

Professor of li-h;~diicall Selenee, iDepai'tment of Physik:llo,gy 6r()w F1! U niiversitYJ Previd ence, Rhode Island, USA

Stewart"'s

Te-xt:book Of Acid~[Base

lill right'S reserved. Thisbook isproeeceed by co:pyriglie" No pan~ of~liis book maybe rep:roduced inS-ilIy fO["111 or by a iII}' 111A.."';l:I];s,.il],dud.ing photooopyil]g~ o~ utilized by al]yinfor.:nrI~tion s!tQ'rcag" al]d~~ru~a.l sys!rem wkhoutpertn ission 6:-.0[11 the oopy:ru.ght own"lf.

Edi~olbl:.§ ohn A Kellum, lP:au.lWG Elbc:I"S Pw.d!~]cdo[la[l..d! Cover Des~g.[I: Pllll..d.WG Elbers Printed ill ~:he United S~1l:tes of Ame.ricaby Lulu.com

St:condEditio.n

IjSBN; 978-]-4!M2-5470-6

Lib.raty of CongtesHil Gooil:w1 Numoor: 20099201U6

Copyl']gh~: e 2009 b}T AcidBase.o.l'g ! Pllim WG Hhej'!$, Ams~~(]am, The Nethedands infO@~J:;idb$s~.or~

The autnol;s havemade t:¥ety effort 10. _provide acc~u.ateinf:ormatiun.including indk:a"liol1ls. acdi\'C:rse reactions and do!Sage schedules fl}r d;[I!lgsanrli tl}era!p~es, HI}'IoVe\'C:f; medidne and biology are e:vei:d~3ingiing fields, It remains the: lesp<lfl:sibil:i:ty of I;hetre~t ... 'ing phy,s.idan ~o check ::.l'nd. determine tndkadons and d08ag'(lsin tfildhr.i!d!ual tailients. Neiifiler the ptl.b1i!iher~ nortfile caitors,n.o:r the a~lii:h.or!ia!isu:me a:rny liability for any injurYO<f d,all1.a,ge to pe:rsl}ns or pro<pe:[itY <lids:~ng from ~his puhH.catron.

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c:m."l:!t': !le'J.'iI apiP'~'fJ~l;:hc5 to acid-base 1ll1le:d:icil1.e ha'i'!;' ahvll!jI::i giv~nrist; trJiilltl;:n5e di5'ct!S5~(Il15, Examples are [he; ,g~eall til:;j:I.1:>l1!tb:nti~ o~batl:: 011. lbsl:: EX"~5, in dle ]'%oJJ.s ~:l.1d a. trc;:ncl.ul!lll dispute on ehe SJtf;W~Wl apiP'~oaJ;".hill the: 1990s;, :[111. the ~"'U~It,p:i:filp():n~ilJtS; of ~be' SltE:\vatll m.dL~m'l!mm.pa:reCI! [h~i.t1iS;E:iJ".~S Ita, Copernic \vH:io \vruS alT.lclIlJJg iih~ fti:8~ ro'i:eaiize d.ta~ the eatth is ilot the C'entet of the l1i:"Ui v "'"e:t'M~, Ti.tis book does n.at WltriJ~ to, IS~l"lJft arcoeher ,ea:r:utoo'~'e13jf, Still, it is: a.hWlYS ... ·Cfjf hclpf, . .!lItO' sec I[[lings fl!oOO ,~ ,diffeicnt peJ:spcc tive, Heaee OlJif choice iOf the OOVeJ: (l1'~ frJf ttl:Ii;, book: "SIIl-nrL5e rrJJI.l1 [he: l'\!J,)():I1" (iStf)o;;Ik[lhotf)/I\.hrk EV"!:I.IS).

170 m'il~'pca[ern5j John a:lilid. Barbara who are al\'vao/s, my greatest sources of :srrength and i:lili:Sp !1'l1Jtion.andi who muglu me the value of asl1:itl:gqooS(]OfiS ,~ Job:g .A Kelb,u:u

To JMIV. foribein,g f;;Ultilrstic- &ul WG EWbe~8

Ayulb, Akbalrij, MD'

A$siistarl!t !Professor 'Of ti"h;:diiciineJ Kiidrney Research Centeli, IlHo:splitall of OUaw~. IlJlnilv,erslity of OUawa, Ointalrlio, Canadal

Rinaldo B,eUorao, MD

IPm:fe:s:sor ofEnt~ns,ilv€l Cam' IM,~dlidne! Depalrtment of [li1lt~nsliv~' Cam, AlUIstiin Hospilt:alr Heidelll)ellQ, Vilctorlial Aiustllallia

Ed B,urdett" MAr MR'CP,. FRC;A UCl Gentr,e fOIiAFiIS!iesthesiar

Uniiversiity CoUegle London Uniited Kiingdom

Pa'ol,o Calzavacca" IMID

IlD,epartme Fit of Intensive C,a re,

Al!.!Istiirn Hespltal, Heldelberq, Viictoriial, Alustl!allia

Peter D Conrstalble, BVSc, MS, PhD" Diip ACVIM IlProfe:ss:orandi Head, Department of Veteriill1!allY Cllif'liical Sdences, !Pl!.!lrdue UriliveliSity, Werst Lafayette, [riidiianaJ USA

Howardl E Corey, MD'

The' Children's !!Kidney Center of New Jerse'¥,

Goryeb Chilldren's Hospitall! Mlorliilsitown, N,e:w ,Jl,e:rsey, USA

And rew ID urwardl .. MD', IFCP

IlPaedi,atricIntenSilV8 Care Urnilt,

IEv!I;liina Chiildlren':g Hospital, London, Urliited KirligdQm

PaulWG EI bers" MID

IlD,epairtmeFilt of Anestltlleslia, [nteFiISliv'e Caire andl PaiiFiI Mlarnagem,ent, si .. Antoniius !iH()!spiitall, Niieuwe.gleiinl The Netherlands

.Jaimes IFi,gge, MD, MB,.A, IFA,CP

Department 'Of Biomediicall SCiienoesr School 'Of IPublk Health, State Uniiversity off New Ybl!ikf A.llbanYf lNIew '¥orkl USA

ILuciano Giattinoni, MD

Proffessorf [lf1!:5titute ffol! AJ'I!es1!:hesiiollogyand Re'aniimat'ionf IRCCS FoU!!rnda!tiiolrn.1 Mlag,gliiore Pollicliinilco Hospiltall, Millalnj nally

IKyilie ,] 'Gunnerson" M D

lrheVilrgli nli al corn m olt'riwea 11th U nliver:sity Rea II1li mati on IE,ng illn,~~ri II1lg and Slhoclk Gent~r (VCIJRES) taboratorv; Dep\~rtments 'of Ane:stirn'eSi'QI'ogy!Criitiic~11 C~r'eand Emergeflicy IM'edkiflier

Vilrgli n ilal Ciom monwea Ilt:lh IJ nliv,ersity IMedical1 Center;, IRIchmond .. Vii rgli ni ai" USA

,Johannes Givan dlellr' tloeven, MD, PhD

Proffessor and Head, Department off In!telrnsive Caire Mlediciinef

lIInliv,~rsity IM,~dii(all Celi1ter Nijimeg,~nSt" Radlboud, rNiljm~geli1l, The' INlethelrllamjs

ILewis J 1iC81p11181n" MD" FAC~S, FCCM .. FCjCP

.Associlalt:e IlPm:fe:ssolr ,of Surgery, Depalrtmell1lt of Surg,~ry, Section of lnrauma, SUIglicall Orlitlicall Careail'ildl Sur'glliCS!ill Emergencie:s;' Dlir'ecMrl Sur,glic~IIn~ensh/;e Caire IIniit; Diirec~orl SUIIQlica,1 Crilika,l Caire and! Acute Care S~rgel"Y Felllowshiipsl

Yale Unilversilty :Sclhooll ,of Medilc1inej New Hllalv,~n, COll1nedilClU't, US.A

,John A Kellum, MD, ':A;CP, FCiCM" IFCCIP

Proffessor of Critical Caire Mediciirn'e, liCIepartmelrnt of Critica!1 Care MledicineJ lIIn1ivl~rsity of IlPliUs!burglh Sdhooll of Medic:in~" IlPliUs.iburgih, P,~nll1isylv2mia;, USA.

IE~lisa ll.iic8Iri'" IMID

Departm ent OIfEnt~n:siM~: Care ..

Austilfi IHolsplita II, Heid,el ber'Ql Vii ctorialAu5tlraii ta

Il..lndal II.. Maerz,. MD, F.A.CS

.As;sis:ta~lt ProfeSSior of SllJIr,gle~y, IIb);epartmeil'ilt 'of SurgerYI :Section of TY~Uimal Surgiicall Oriitiicall Care and Surglii,cdlll Emer'gendesJ

Yale lIirniiversiity :Sdhooll 'Of Mediidnej New Hila!v;enJ ConnectiiclutJ USiA

Sheldon Ma'gdlellr', MD', fIRCP,(C)

Proffessor of M'ediicine and PlhysiiollogYI Diivis;ion of Criitiicall Care.1 MlcGiillllllniiv,~rsity IlHeallth C€Hnltlre .. Mlontlreall, Qu~bec, Canadal

IB8!r!Ii"Y ,A, IMliizoek .. MD' .. fACP, IFCCM

Dilvision of Pullmoli1lalry allnd Criith:all Caire IM,~diiclinej

John Str'oger IHospital1 'of Cook COilmty, Chiicag('1, [Illliil'iloi~h USA

T ,John Morglan, MD

I ~Ite nsive Caire U nlit~

Mlat)er Adlullt IlHos:piitall, South IBriisbane, Q:~ee~island!J ,AlUstrallia

Mi~ri~aim M,ovi~art, IMIID" IPhlD

IlDepartme rift of Intensive Ca re M ed iieii ne

Uniiversiity Mediicall Centei INliijmegen se. Radboud, NijmegenJ The Netlh,erlali1ds

Monty My then, MD, flRCA

IlPii,')rtex IlPi<)f~:$:s:or ()f Anaesthesiaand Critical Caire, Unilv~rslity CojU,~gle London, Unlited Kilngdmirl

1i'loel:s, R illl"EI, IMIID

IlDi~partmeli1lt: of N,~plhmllogYr

Aalborg IHo:s,plitall, Aalborg,. Denmairk

HenifY Stiimipfli, DVIMI, Df'lMled Vet" D'ip .A.CVIM

IlProfieSSOir, IlLarQ,e Animal MedilCline1 Depairtment .o:f Clilnilcall StlUlcliiesl

Ontarlo Veteririia,ry Coilleg'e, University of Guelphl Guelph, Oriitariio, Canada,

Peter .A. Ste,wart, PhD f'

Il?rofe:ssor f.Jf Mediieall Sciieln,ee, Department of PlhlysiioIIQ!;;ry, IBlfiown IJniiversiitYI Providence, Rhode Island, !LJlSA.

David A Story, MD

IlProrf~:$:sor of Anae:stlh,esiiaj liDepartment !lJf Anae:s:t'h,esiiaj A!!JIsitilllii Hospital, HeidellbEH'g; Vilctolrlia; A!ustrallia

Shane M Tibby, MOl, MRCP

IlPaedatricEnmens lve Care' Un iitj

I~veliina Chiildren':s HOSpiital1 LOrldonl Urllited Kirllgd('1m

Peter Willl!cest IMIDt IPhID" IFRC~PC~ IlDi~partmeli1lt: of cardiac A.li1lesth€l:sia,

UnilverSlity of Ottawa IHeart IlrnstiltlUlte~ Ottawai, OirntailriO, Canada

[TABLlIE' OF' CON'TENT'S]

Wihyai!i!d Ho,w to Reaidl Thlis Boolk

Practicall and Theoretical Aoid-B,i:lISIe Physiology [WIre-face to tlhe IFlirst ~d !t!on]

[Foreword]

In Memory of i?ete'r A Ste'W;;iIrt

"'Hlow to Undel~stand Aci~d-Ba!se, a Q:L!llantitalive ,Aci~d-Ba!se Priraer' fin Biioillogy 81nd Medliicine'''i SteWCllrt's Cillaissic 'Text

['lntn'JdlulctionJI 1. lBody IRI Uli ds

2" Goall s, Defii niltlio!f!S and Bas!c P!l'!inciples

,]," The Simpllest Add-Base System: IPure Water 4. Stir'Of!i,g l'oll!ii: all!d the StrQf!i,g ]~on! [)in'~ref!ic@

,5,,, Wei:llik Ellectrollytesi:lll'1 d BuUers

6" Strofiig lOins pilus Cairlbo!f! Diloxil,de

7. Stlrolil9 Ions plus Calrbon Dioxide pilus Weilk Aciid 8" l!f!te!l'aiCt ions b etween Bodly lriluil dis

9. Whole-body .Add-Base IBal.~mce

] 1 n 1

[P,art: II]

Q:uantiirtative ,A,cid~Base Clbe'll1li~stry alnd Physi~olilogy

io, lNormall [[SH>]

n, Rolle of rNon-Volaltille Weak AClids {Alblllmlil1l, IPlilosll'halte and Citlralte) :!l.2, A,dIVaiil(jils in Es,tiimatililg [Awr]alilia lK . .o;

rs, 1I1lltracellhJllaii [IHI+]I

:!l4. Basf! Excess

15. BuU:eFs

:!l6. Pn~g iiI,am:.y

]7. COlmparative Animall Physiology and Ad.aptl:lltiorn

201 2.17 23<3 247 267 .281 29'3

31(],5

Clinical AIPplic:::atiions of Q:Lillalnti~tative ,Acid-Base Medicine

]8, UfiimeasUiredi Ions aind the Strofiig Ion Gap ]9. Using the Stewart Modell .at the Bedside 20, fluid Re:slIIscitaltiofii

21,,, Hyptifllfchlloremi.a

22. lLalctic ,Addlo!sis

23. lRernal Failure

24. Re !i1a II ll.!! !bul air Aclidlos!is; 25, TI1r,~ lLiiv~1r and the Gut 26, Sepsis

27. Trail!! mal

28.1he Emerglency Dell'alrtmenit 29', The lPi~riioiP€l!atiiv~ P!€!rrioa

30'. lPediatlrics

323 339 351 365 375 39.3 4~Jf 423 431 443

4S3

46,3 479

[Afteliwordl]1 [:[nd~~x:]

,4,99 5~)3

P·auIWG Elbersand lohn .14.. KeUlum

Add~ b;il,se equi~,ib[:iut.n is :a l:llivQtdwp:ic~n~hr.; biomr,;d.k'a~, sdenQr.;s ~.tld i!;lh]iJ:;al, In'l;dJdne.

Studied lbrlut:c:~tt'3I]r m illiDll,'l of pc:opk it is ()i~tc,[Ipc[cdvc:d as diffl(:ulit,. 1'hL'lm1l!y be because [1 commonly rt:;mghrt aJppwll,ches toacid-base phys:OCl.~og}~arewn[~si:'-Ig and illogical, Akhol1,gh these methDds are n'lJuhemll,tically eorrecr, nuny will recogeise the frustrM~om that~ come wi I~~n~iflg;il,ndlll,rpiring th~m, T~ey f~C]~[Idy i!;,~:[1 giw~ise ro dlf~ul;il,If"~~solJl~[Ig :and tiring dis cussions. BIJ]il:wotst of 1111,. t~csc methods seem to need adaptations 0Itt" p~ug.i.[']"~ to be: of usc i[J sumatuom thai! aJre slHghtly mote complesthan standard,

The bJl;e Peter s~~'J;~lt'e:slr.;~J:;y is ttl h;il,l'Ile~~lI,]ght thousands of us th~t ~J:;Jd~·base kihysiol. ogy doeStiI£J[[IcoD,mobe. difficult .:It all, We: are .... c,[j' gmi!efuj toh iswHow, Babette StCW';llttt(J! g;Jrn:'-Idn,g us t:llecopyrlght to hisclassic t:e:loi:tbook "How to Understand Add-Base".,

Using Q[I~' h igh ~I~Q()~ !J!lge~lf;l, S~r;",~f'~ dr;tnysdEues ~dd.~~sr.;phy.$iology;. !J!nd he dor.;s· so i g YC[}, eleer and concise stylc.We h1l! .... e grca[ly elll~o.ycd his. book and decided roUe:.:Ive:~t like it ITt has become the first .pcan of the book )~ou are holding (Onpben 1-9) and. we aJre sure you \'l. like ieeeol

N~wltI_I~' you should S~~~~ wkh Stel;xrarfs 1:;1!J!5:sk text in Ch:apo;:fS; V), You will fund ir Jsr.;!J!~ toread, The Most i,mpottam[ :advio: fot rou Us ito, at ]C.:lSt ite:mporn[Unr~ fott"gct,,'VIl,la[ you altt.:ldy knowaboutacid-base phys:no~.ogyafid :medk.i'-le. Opponents .o:[~he S~ec:wart appwachrr[el.ll1.efil point: oue dlM~ the method is d]:fficu~~ teundersearrdbecanse it requires many calculations, 'T.~ is ]'If)l~ our experience at~ all. In fa.c~. most difticullties ill tUldeil:st:llllcliit1:gandaccep~ing theva]ul of t~e Sre'Wartappr-.o!J!ch stern rr-om w;iI,ifltiflig ttl c'Omp;iI,fr; ()!t:' r-,el,lltr;ut to the more tltldutiol1;i1,] teachings. 1'hL~ wi:lli:[J)e:vii:.:Ih~'lc-gd~o ·crnt~lI;.~in[l and more docubtfeasO:[Iing. Thc;tt"efD1tt"e·\Voi: et1aou[:iLge you ro start with a bbnk slate, Ym.I wUl be rewardedl

I[:L4)

FiOR. TlHOSII!! THIA1i' AI1RI!!'ADY KII'!IQW ABOUT THII!!: S'li~AIR:T AJPPRQACH

Suttt:.~y" }'fJ'U ate v;rcl:l(J'111C to re-read Stewarr's ~!rig;~fl.",l tCKt~o f:tt:ihefl. Up YOU!: l11CruUUY, HQW~ tV,er, 10] m.ay"!liJJ:[IJ~ ro jump Str:a~;~l~~Oo t~e second p1l!Jf~ of our book:"Qu1l!:ntD~1l!dve: Add-Base P[l}"$io~ogy and Chemistry' (Ch~[jl'ers, 10-17). The last 25 re.llr8 of lliC~vrances, in quamit~t.i.¥e acidbacse phrs~doID'hal'lle beenreviewed rOI: y0~ by tQPtEes~ari;:her.s and d inieiaes,

A~~ero:;tti\'d~!yaa flUty' 'W:ii:[lJi! to proceed dif6cdy t()~he hst p8Jr~ of OUr book: "ah1ic:;i~. Applications of QI].atlti.t~tive A(;~d,- Base Medicine' (Chapters ].3-3Q), This seeeiontakes St~il:t~ eo dlebed5:ud~ by IlrlQV~d~:(]g 11racdc!J!111Ie!J!l1s to use th~ap'P.I:i)ach. In,add~.t~,o[l,,~hef~ are dufre;f1l;:(]iJ; chapters fnr virtually allfiekls ofmcd.idnc""vhkh. yuu can either rcadGorti>cclJ]tivdy or use as '" reference for ~~OU.[ spec. tie du:nic:;i~. scenario,

The S~e\V"JJ:'t approach has been s-ubjecct' of fierce discu8s~om: and virrielie debases, For us d~]s means thatthe .sll.llbj,ect: is .import1l:llt: oolImny. It: is nm OllJr int:en.ti.o.l1 t.o M~r~ anothercorreroversy; 'We jUC$t want yQUW b~u~r~tld~:rs~~.tld i[:h~ 5ubjl~ct a(]d~1; th ink tha,t the Srtew:a~i[: app!:{y,l!;::h win ce;[t"'~nly lhc:lp~D ",.chic:vcthis go",~. Intl:;ttt:,~t~ng~y, qlJ]:DICC a fi::w !Jnook",l tCN:tbo~i~:SlJJimv think the:

S8ime,. introducing the Stewart ·:;tppw1l!oCh a:> the method. ofcboke. This st:re:[lJg:the[IJs ourbelief dla~: rhis book ]8 fore".'eryone t~a~: has ~ny~hing m do with acid-base,

[PREFACIE: 'T'O' THE S,E'COND E:DITIIO'N] P'ral,c'ti,call and Theoretical

A.c:'iid- Base IPhysio,llo'g'V

John A Kellullmrand Paulll Wei Elbers

'W:I:l:en wefiJrs~ considered creating-a seeond ediidorll. ofStew:a:rt:'3 chss;h:: "Howto UI:ld!erstaJ: hieD-fuse" our tllOl:irvu:.ilon .."hlS solely ~D ]n!pt'Cl1u:e irs accessibility to a gnnr][)ji!; fll1!mber of 1jea, ~~, HQl\.v~~f',gS W~ b~~[1 eo pb:[I fo~ thisr;.d.kkil[l. W~ b~ii;;~m~i[lii;;~~$i[l~y ~n~I;~stOO~n wh~t made: the: o.[.~ghJi."ilI. text so [lopll~.a!t and at the same rime why.k produced such n.e::gadvc reactio from SO:iJJ:1.C quarters of the i1Iudctnnc wotkl. \eVe:: suspectedthat the:se tWD oppos:utc: rcactjnns fi'1ight be closelyrelsted to the SUllie rooresuses,

One; of the fe:!lI:IJ]:(C..s thi1ll: attracted 1&'> to the:: St~rt ltimudd~ms iilS shupHdily and dmu.l[g.f1~ t"flls.~y its comptehenshre:nes:s.Oas::;ic:al :lI.dd . -base te:llchung emp'lf.~ys the Hendeeson-Hasselbalcl eqJU::1l:.ilon for classitication of add-l.'mse disorders mw respirnwry (CllLbon dioxide is abnormal' and. metaiOOlic (bicarbonate ]S aibnormal) and defines a frnmework for eompensatory d:u:lllgts the v~u~lblr; d!r;~jlled(]o[l~plfjjllaly Next, classical reg,,;;h~(]gr;j1ilp.lo}'s eithers set ofsd hoc f:U~e. or, more si.i:np~r, base-c:xce:S:llh(le:tl1odollogy topll:zzk OlJ]t Hlmplc:x d.bDl-dcrs :and I:oguultify tJ magrll.im&e of t:beab.no:tfi'l.a~.~.ty. F.i:ilill]ly~ cbss~.c:al te;ac~i[lg employs 1l. Umn~ed. dliaJ~":t e~rll~.~~b:riflJ.r. meshed (anion~p') eo help narrow thed:iffeilemia[ diagnosis, Compared torhe unifiedtheor of the 8tl;~fl i:nodl~~, th~classk~l applfoach oertai[l~y S~~l11S ~[I~l~ga(]t, MOlfeQve.~, there was a need I:Oplug:va:dol&'> lleaks in the cbssi.Gll model w.ith more ad hoc cu!::tc:niOtrlB.Fo'[e;xi1Itnp.Ie:, a:nconWJ!p assumes a . .rII.e:1r[llYrmaJ] concentraeion of a~bum:un and phosphate. Wherll. these 0011- centrations are nol~ normal, the anion gt1l~J has, eo be "corrected",

In conrrast, the: Stewart modelrequirea, to use a term of {}utiJltc::r[le:Jt ggc,no '(p~llg-im~"" [.1 addition. the Stewart model works in aJ]l condirions [llY~ JUSt thosecommnuly fml:ilid in medicine. This ['eil:~u1jethat t1~e model holdseven eurside of d]eciinical .range did lit~[e to imp'JreSs d..e'tl:a.C'~Q!l'S, They arg~r;;d tba~ a model that has uti.liy even wh~n we dQn"t m;,ooit ~s [lot a bern model and tmgge:stcd thar the w:ry act ~lf showi:n:g: th!ll: the mode] p:tf.w.~de;S 'il .. ccurate p:rc:d.i.cilioj in highly [llYn-pbrsioJJogjc1i~ states isevidence that it is .rllo~[leeded" We respectfully disagree aJ:i point out dual: if model does fim hoild under extreme conditions i~: m.igjh~ noe hold at. oehertirr ;l5.WI;lt A law is nota lww wh~11 it ho~d!s true O[l~ so:m"dmr,;s,

Howeeer, alm~lchl)igger dlaJ]lell;ge to the S~e\V;itf~ .model haJs. come fwfi'i. the empidca~

[[16]

sid -or more pm~~i,sely fro.lTI.e~)]S:l'e.!nQl\:lgJ' U~he :S~e\VllJ:l:t n'l,o(re.[ ~}redlicts tharchanges ]:1:1 d:lie ~'l\mporii;III)i[l. of an:nons ~ndC~!10115 willresult jn changl;sun pH, then we wum havc;w c.h!l!nge

QUI: defmitlons of adds ~nd bases, The pmb~etn is lh;IJt the Sl:e'WaL~ nlocld~e~r;b to cO[lclusions il:h!li! J:re l!:umpleJ:e:ly at odds with the S[Jt:us quo - J~[htJughnot so d~f[e;tt;nt f~:llm how acid-base was underssecd 9!S recendy 3S the 19605. For e~9!fi'lp~.e,~he acidosis that results from dilution of plasn1;a. wid'] sa]jne (discussed in Ch .. prer 20) was described ]11 Cushing's time butthe eJlp~ a uail;I01.1 for the Ilhenornenll)i[l has new It' been endlt'ely established, [iII the "i[lOW il;radutlon!lil'" model, sJ~~ne.reJsl[]s.di!;l[[iOfl results in J. d:Hludo:n of p:~!ls:mJ bicarbonate andwhen PC02, is hdd COns[!I:!lit [by respJrn~k.if.'ll, art alLndo5~s resldts,,[:':Iawe-.;ret,ut seemsi.l]ot1Cllil fOf dUrrndo[l orlb~.cadbo.[l3i1:e to result in ilIcid.osis when reducingessbon dicxide results in a]kalosis, After llJ]], they are both just fbmt$ of ccaibQ[lkadd and. h '$t;et11;$lnrupmb~b~e~hauuht;~a1(ll,,' ofm~5S aCdon\lllQu~d '$t;ind still in il:he:cJSi: of saline resuscitatjon,

AcOOlldil'lgto the Stewart model. the llJddi~ion of saline results ]n a reductiea .. in (ile strong kll[l d~:f[t;[t;nce (SID)"~ccaucseol1e :us con~bin'nga 'soIu~io(] wu~h ~ [SJD]I (lif[-o~ghly 40 111EqJ/L {plas:l11'a) w.uE.h one that has a [SID]I of 0 (sJ]~nc:). The: mudd ptc;dkts il:hgt chJnge;s in. [SI DJ wi.U result in ~hiJJ:nges, in pH. Tho; problem is t~iJJt dl:1nges ~.[I. [NiJJ.~]:1[Jd [G-]a;re not supposed toresu.h~ in changes in pH, I[N~:C"j and [Cl]alle not acids or basesand thus llJdding the.l1flto a solution shomB have ilIO ·effect onthe pH, Ye~. as ,I;r~ have ~.~.~ ob~1"'>1l;d, th~pH ch!l!.tlge5.

Thisapparent PiJJtiJJda;.: h9!s problems forepiseemelogy but ,\ve shou]d [JOt betootroulb~.ed

ib}T theru, ll,s scientists and. cl]nicia:l'ls\l.;oe. don'~ E:mue to underseandwhy something is ]]'Ji. order eo clet~il:i11~:n~ dl;lt jt~8.Th~ SiI;e'\;v"il:t: Ill0cld p1"clk~s dl"t as [SID] c.h!li.nge5 50 roo W~.U p[-] !lind QUiI: expetk!lice: HJ:IJJiHrms this. It is thc.re.fim:I1Dt~ngi.Cill W condmk that because we do not understandthe mechanism whereby [S~]Dll changes pH, .k >L3,[I:not be SCi,

S~l;'JI"'l1!:~~ hYPQ~he5Jzoo~hat Wa~t;t' dussod!liteS it1:~o H+ ~lid OH- to a g[e!litl;:r or !Ii l~ssel~r;Ktl;n~ when [SID], [Arm] o()![ ·lPC02 ch'.ll:n:h!\:. "Ill diJ,tc there areno e;ltTIlpi:rk!l.1 o!bse;tv:ation~~[hJt: ·confiirm '\oV:a~et d:usrod9!t:io[l as the f.I]eC~3[1:~5fi'l.\1,1he.[elby I[SID~., [~_,,.II or PCO~ effects pH andstudies of water lartice under oondil:ions of varying lSnJ], in fact, 6-u,WS~ no suchrelarionship, Thus. the Ste>,varthypothe5u8 has no empJlt'k 's~pport This does not in ar.uy way inV;llldate the model or GllliniDo C]uesdon the; OlllJtput uf the: model howl:'vn. }\'HhDllI:gh c:xpe~[ne;nce; h the ~J:!li]r judge of scientific theories, scl.e.[lti tic kf.'llo'\vledge does, not ,e~drrnsi.""'"ely arise fromexperien .. ce, Sde[lt:Hic ~:heori.es are gt:l'lU]ne hYl)a~heses~h1l:t go beyondthe Iimits ofllnire human experience, In rheolletica]phy:sics, for example, models Df the universe require extra dimensious - yet.~here are

no obcset'1l;lJt~o[lS that havc;be,en Illwe th;IJt lOl;(juh:er;Kna dlmt;nS!QBS, 1'h,emodel'cs 'soundness hi IOOse;d. 0[1 .. its abj]jty~o make 1Jite;dkdon~~~n[he; obse;tvillb~e; wodd !IS ,VliH as the; worldwecennot observe . .POt acid-base phy:sio.~.ogY' we are f9!f more concerned w.ith e:l-ipb~nilt'lg the olbse:rv9!b~.e world, Om observation eh a ~ clia:l'lgts in [S]Dllllesu~~ in cliill:l'lgtS in pH mllJ)' noe be expb:ini1llble bywS,.l\;r dlscrod;IJdon but neveetheless the obseiI:V~tu011andmod~1 which describt;5 it cca(]nm"~ discarded,

Threughout this boot. we refer eoehe S~e\VilJ:r~ hypo~hesisasa .ready expJa:l'lilll:i.on. ['01:: the Ob8eF'1edassoda~bn b~t~'\;en~he varia'bl~s [S]D]. [l'~'r] and [:)C02 a[ld th~ var~;IIb~t; pH. We

(17)

recoW'l.ize~hllit ehis rheoretie Con8~:"UC~ ]8 .only one of a number of l)Oss.iib~e explanstions, Inour experience thl)qJ!gh,~hel]qJ!m~.11mil);dI r~qlllire$ an eXlj~al1iaJt~ol1J forthe pIU;'I1JCl'l1lenl)n we observe, We!ind it easier toeemembee rchil1Jgswhel1i we can aJt~~ubutt; :a c'aUS!l;.l~ink,Wl1iiUt;r.;l:!ilpi~k~~ evidenee has ODE been fU~:[Id ttl s~ppo.rt the:: Stc:."vgrt hypotl1ic:sJs, n-o clear d~spwof yc:t exisn s dtl1c.tt". Tbus, 'JIlt; offer theh};po~:he$U3as. JpotendJ] explanation but more in'ilpOhundy d~rec~ OI.l[ atten·~i.oll. mthe modeland irs use - the pnu::ti.c:alappJ]cM:ion. ofthe modelas well as the eheoretical, A~dlJough we cml1Jm ye~ d!t;termDtlr; the cause, .. ve aee neveu:lldess ~Ib~r.; H) usethe :mode~ rom~.kr.; prc.dkdo[ls :an-d. the: lIcc:urnc:r of the'>!: p:tc;di.dioa s is tile o[lUr trm:: tesE ofth~ model 'Thu ... fat, the predicdons have been sP'Ot on.

[PREFACIE' 'T'O' THE FIR:S:T EOITIIO'INI]

Peter ,A, Slewart t,

TIle approach to ~:[ldle:rsta:[ldI~o[lg hydmgen ionbehavior that ispsesenoedln thhboo:k has been develeping ever since, as an undergraduasechemisery major, I firs~ eonfroneed the cenfasbn SIl,J!.lT'I}lI,J!tld.ing biQUogk!il..l uses of the teems "pT-~F'ail:ld "buffe:r/' The d"fiv!iL~ion~!il.iI:ld d:~sa CUS5j,o;[].~ always seemed 50 drclllLlll:tt" and fru..<;:[:iflI,d:llIg. No ge:,fleltal :ltlS-vcr W1I5 ever ghlcn to the questioJI '~W1:11t L~ut dli!llt determines 11rrd:roge,n. ion. COJlce:.m:rnltioJI. i:Hli. 11. 501udon?~' and! thllt surely is~he first ll1.1esdoit! When" 1JJbotJJlt 1973, ] fi.naUy worked OtH the:;i;."iI:Oi:'iishing1'r 3~.ltip]e an ... wereo thll:~ question, computers had arrived, 01100 .it suclJd,enly became easyeo use the answer in sarisfy.i(]~.y lll:!il.ctkal ways, ConJl;~:n,uing fecedback since then,. hCHU c'Oll~agues ~nd 6:0111 glladlu~JI;e,dj students who 1IOC now p:rncddng phrsicullnS:.tt"L~~atth scienrlsts, '.1I:Hlid teachers, has reinforced lIly ro.rr"icdon d11JJt d.o:ung hri~t is mneh easier dnnut looks, and thM undJersunding is more PCf\'!!erful than memorized formulas, A result of t:ha~: eoevictien is thatthisbook is most rewarding \~llb.e[l sl;lI,J!;;:H~d and d::lQlI,J!ght I;h"Qu:gh,l.':liL~he:r~h~.t1 jIIl,J!St[~,

Because this 1JJpproa.ch is so d ifmerelti~ from the ·dasSiUCJ] and historlul . one, I have tried

to keep them separase, a:l'lld eo stan fresh and unclaeered by the ]]m[~M~Oi1:lS .of pneCoillputer. sd~1'lce, ne,sp'h~ .I:n~:[Iy u~ungs,. I have the[~fu[~ l!il.rgely omitted l'l;re[l;nlCe$ ro the hJ,~rol"kal d,c".'ChPIne:,fi[ of"ilI.cid·base"' iHli. hiolof,"Y '.1I:1lI.d!n(tcdlieine. I hill.ve:: also !lsllu[l(J)edl. that :I:!liymie who reads thhboo:k will have S011LiLe useful.ac~ual.nltance w.it.h general chel:l:'I:istqr, bialDgy~ J:[ldl. mamrnalian physiology; 00 thi1l1: references to particular t:ex~tJooks are not: needed when kidneys, lung.~, oslnol!il.lt'uty, and so fOf~h a[ementlone,dj, For beth these reasons, a~mOM no~fe[enc:es to the Iiterature are p:tt"Ls.enJtM. The development of the subje::c~us suff.ndcHlitllr self-contained that: de~J:iledl. references s heuld .n.o~ lbe needed. at this stage,. \Xfhef.'ll they do become necessary, readers can supply their own. fromthe eeormous relevaru literature.

It shol[]oH also be: dealt from the: hcgi:Hli:Hli:ung thatthere hnorMHlig sacred, gmu:'i1I:IlIJtocd, or abso~mealbout the m]:metk"a~\laJl'ues. used. here, Inmy own perusal of the literature, I have been ami1l2eda~the range of valuesquoted as "true" Dl1' "correct" or <"i!JeSt:."f'rOltl thll:~ ra:l:l.~, I l~i1Iye as:~l;fllIWed some idJosy[ll!;f;lJI;i.cal1y weighted al'llel:'ages 00 use he[-,e, ]f }'QUi don't Like any (lif the[ll., pUellse use your oW.IlI. favorite wlil[]cs. lP.tech~e::llIl1lne::tt"kll.1 '!l3.klcs,even if theY'Nc,oc m,eaniHligful" are not rhepolne Clf~Ms, staqr. The resultswe get. a:m~ the prlnciples jrrvolved.are il]t]stt:;)Jt:ed lby

tile .Inlltly comp~ter-plmt~ cerves ehrougheut rhe.book, AclFllJ:s~ing t:he:ir scales 100 fi~"be'~t;e.i" or ·'l:ncr;f.en:"dN par¥tnetel: va~l)I.es 1;S e~5nY!il.'C,()o!l11p~is~ed, and win nm aff.i;c[uhe al:gll.l!mr;nt8 or conelusions,

So nu,n}T friends, crirics"and fellow seudents of all sons E:hwe con~db~Jl'ed tnthe development of this book t~~!I; ~t'>J<'Qu~d be ~m['}L)5Sible to!llciknQ'i!,di>edg.e t~ej]l a~l It is also diffucult to ranktheir conrriburioas, Sometimesp .. gcs of d.<::1t3:~Dcd ct~ddsttr.1''i, S0111Cl:i:mcs [ust a few easuel words at [ust the dg~tgluestbn ,VCfC neededto u[I,lock g~nIJlW,:t"[Idi[lg PIiJOfb]cM. ~T gmcxtoc[[(l!dy gt:!JJteful 00 all who have~hu3com:r,ibu~ed", None of them" of course.bears a:[ly[espofi~Ibilky fur t:he remaining defects, Special tfuan~s ITmst gp too the 00]] OW] fig who have providedcrucial hclp Qfm~ny 'SQ!r~8; V, Feild. Q. Fil~~1. R, E, FQrs~!?r"f!;M. G~~~~t~i, J,Gan~bl~, 'L HQj]l~r, D, ]~J;;ikool], N. Ki[ldig:,. A.. fJottcl3, B", [te;cvc&. and B, 1~" SltCW\'lif[, 'mJ.I1Pa~a[t andWa.)"n1ic Thorn.lbl[]rg, barb now deceased, provided wnti:[lJuing st~iI1L1LU~.a~ion a:[lJd enaou'[agem,e:nt. each. in his special way. They are sorely missed,

LLlIlci,ano Gatti~noni

When Lfirst hearda lecture all the physicnchemicalapproach to ildd-hase e~nmbdHfi1 based Of:ll. Stewart's, "'1Ort my tirs~ reaction was: "a:l'l.OI~her useless and. comphcating addieion eoan a~ID;adl~r diffucult topic", After swdyil]gilt:, hO'>J,.'"l;Vl;f', If:e~~ize-.dI th~t tIll; Stewart!ll.pln"Q~ch~s tile best way~o understand and :tt"l:l11cmilxt acid-baseequil ibriil]:mpcr se, :allld,. more~m.pQ([lra:r.JItly.D[S tt"l:ladormhip with another key equilibrhun of]wi:llI:g Q([bf3:r.JIisl1L'l,. the docu::o~yt:cs.

Ml;d~Ol~ studenlC~bump into dl:r;:add·base l;q]UiHbdutn seveeal times thwu:gholl,l!rt theirccuese .of stl[]dy, .i:r.JI.chemist!::y, lbinc:hetnhuy,padln]ogy,. elinics and during the poo[-gradu1l!Ite courses, p:::u:tl.ctlbdY when the aClue stage of illness ls the malo. topic. Untform:n:iitdy~he :add-hase equilibrium. is usuallr fotgouen as many tirnesas it~ is taughtVsual[y; the ~:l'I0declge ·of~his wpi~

is Iirnited eoehe realieationtharplf may indicasealkalosis or acidosis, tha~~ Base Excess may asSf;$S the fm;taibQlic:addl.osu5/ailk~.~05US. and that PC02 changes Illay be $$sQda~r;dwhh r~spul1aWry ch1l!nge;s. [Ill di ffe;:ti:.tJ:[ ch'.ll.ptt;ru of thdr physiology ttxtJbooks. these students siIllldir de::c[ro~rte; ~ui~ib[ium, learning about oolLlcepts such as hyper- or hypo- naJtremb, -chloremis, -kalemia and tfueir dini.o(;a]conseguences. AdclJ-·base equiihrium and. e~ectroJyte eq]Uil~br.i.u.lnare tfuen taught, a(]alyz~d, leamed al1!d[Ol~gouen a~part ohvro d.iffer~nt wodds.

TIle great merit of'Seewart's phrsDca]-chemucJl approach I;S to show tlJt Jdd-Ibase and dectm~ytes ar,epal't of the sarue pieeure, ]0 a painti:l'lg the det;ails may bebeaariful, but ifthe deta:ils aee cQl1!sud.ere-.dI Q(]~.y by t~'1em5elves one Clll.nI]Qtappr~datr.; the who~e scene. ]n a[la.~ogy,~Qoking at LernOlron's :f1l!11101Jl..'i pain[ing '''"I"Ile:: La-st Supper", the disc:uss.1o;[J between the three Apostles on theiiigh~ or on the left corners does. not gl.ve 1]:5 the whole pkmre,. ] believethat SteWiln~s 3ppm:adi gives us dliecomple~e pa]n~]n.g, whjle oeher appmadies. give us only the details, While these Qdlr.;fa:rp~iOa.c:hr.;s de~c:dbe the s.atnr.;[t;~.~hy and ~:lfe teue, Qn~y the SrewUii; 0I11!t; pmvide$ a tool fOI[ff;llllDy I:I:r.JIde.rshmdi:r.JIg of~he p:too!b]em.

\Wllia~~ is ]mpo.rt:a:l'lt~ ill ehe "beautiful mind' ofthe physi.~och.e.mica~ approach is, tim~, the dis~uil1cdon bet,,;J,'"l;enil1dependel1~ and dir.;pend,enrt v~f.uaible!l. second t'hr;:r;:l:nbr;:dding ofuheadd~ basecquil ibrillltn .. i:r.JI. the:: gelllc:rnl cquil ibriillm of walter g:r.JId. dccuolytc.'l. Stewart idiCr.JId lim thtt"ee independem varhbk:l whh::h filay change the hydrogen ecnceneration :un~r;a,te[ (ie.~he acid-base

equi~iibri.lI.lm}:the strong ion. diffellence (SID):,~he toeal \vei1lil>:acid cencentration (l~OT) and. rhe PCOi (whkh. Isnmhil)g else ihana diffef-,enlt expf-,eS5.~on of !I!.nmher wl;!I!kadd. the carb011k !l!cid). The c~~rlQng ion ditIi;n;n<ceu5 n;gulll~r;d by the kidn~, weaikadd ClQncen!;l:1ltion pri.tnari~y lbyHvl:;t,. peoz br rbe hll1lg .. AU the independent w:[iglbk, J:[I:; pre."e;nt in C{ll1lce,[IJt[;,t[io;[J~" on the order of milmimoles or mil~~eqt]:w:;tlelLlts and their ~nter:1crt~DILI whh"l1iJJri:er dictstesthe amount of :f~ee hydro~n ions, the wncentra~ion. of which is in the order of nanomoles,

The bes[",my to understandthe atchitcctnrc of the St:e>".,.n:'s mndel is m visualize J. histogramwith two columns: ollie ~.ndLudli:lLIg:;tU the strong ions \V.iith po~;utive ch.a[ge.:;trJd~be ot~e:[ one with 01111 the strong ]OOS with negi1llive charge. The diffe.rence in electrical chi1l~betweel'l. these t",,'Q CO:ll[]mns is ccaUed c$t~Qngi(l[l diffef-,ence, ]n normal plasma this ~:mOl;il:nlts to ~Ioo~t 42 mEq/L Indleoo" JtolC'.1I:Ch. the dccttonculi::rnUty;, 42 :mEg of :[ICJ301dvl::charge;dI. ions, d:~f[e;tcnt tilf).m. suo.ng ~0Il1s.:;t.re[,e~Lu.i:fed, These 1l,relbasJc1l!11y~he b~.ca,itboillll!te (HCa,» and the negad\le chaitged :fo.rm of (he weak acids (A), p.ri.mariJJyalbu:lllJiin plus an estremely small amount of hydroxy] (OH"). The CSlllm of [HCO!l-] + 1[A-]whi:e:h~qJlusJ~~ht; cstf.QngiO[l d:uf[~I5t;nc.e .. vas ccaUed"Buffer Bm,e"b}' Sin.biICt J[ld l-tilcsdngs, :iI:[Id lah::i[ hy S~gg:'<latdl~AndJe;ts.ctlL Indeed the b~g difference hetween the Sigga1l!,rdi.-.Ande:rsen.'s approach and the Ste- .. vart'S ll,pproach is d]JJt the fhs~ considers what happens inside the bufferbase doma:in .. As an example, in the Siggaud-Ande:rnen'i> mood th~ (]Qrtnal buffer bas~ (42 tnEq/i.. ~s the n·O!l.'l11al [SID]Jmay decf.e$$e by ~~O mEg/I..~.f the I[A-] JndJ [HCO~ -] are 'oonsl:I:h(l!e;dllb)' gddJ~ng 10 l11Eq ofH+. Iu il:h is: case the actua] bUlffe:[ base .is 31 mEq/1L 1l!:nd the differe:nce betweenthe act"(L1l!]~:mfmet base and the Ide1l!] buffer base is et]l'wl to -10' m Eq!L, t:fu.is, diffe:rel1ice being called t:mse excess. In the Ste\V"lllJt't model the same probk.rn

is considered from another point ofvle\v. Ifa ,stto.ng ion.]s added to the SYStNU the diffe.ren.ce be~wee;(] the ~OCQoIUj]lns dl;mges. As an examplt;,.add~l:lgW m'E-q/i.. (lflac~;lJte the S'Cf.{.l1'lg~Ofl dlif{e;tcnc;e, dJe;Cifeg~ s es I"Wlll 42.mEg/L ttl 32mEq/L The "space" <Lvg~blbk ff),[ A- and HC03- 1l!n.d 01--[- deereases.jndeed p1l!:If~ of Awl]] become AlI,. pan of HCO:~- will becomeH~CO, aI.'IId ~.)J:rt of OH-wiUbeco'rn,e H1o. As thepmduct of H+ and 0[-1 is conseant, a decrease DfOJ-f w~.11 C(lIT~s~':Iofld~Qo ~nu:r.lc:reas.e of H\ i,t;.addoS'u8.

TIle di31l!dlv;a,llIt:age of Sigga1l!:rdI-Andetselll's approach is t~lli! it implies lidding or ~mhtt1lc;t~[lg Itt to the solution, which. is ]rnpossibk The more general Ste\V"lllrfs approi1lch explainsthe acid~J'J;$e v:a~iatj,oil:ls 001:1 a IllQr-e vall[]aMephys~c'al. bilS~,$. As ;:Ii.n eX'ilm~lUeadd~:ngpul:e Wilteil:~O ;:Ii. c$oh,ldon un whjch the s~m[lgbn diffc[c[lce L~ 42 m.Eq/l. will decrease [SID]I,. while 5Il1bt:[gc~ung PU[L \V:a~e:r willincrease [5.1DI., In the firse case 1l!cklIosis develops.mthe second case alkalosis. The Ste:\l,rart)s app.roadiba;sicaHraUow.s one LlO und.e:fstai:Ki. the aeid-base e~u.i]:iJbr]lJjm considering \Vb~t ent~1:S the ~1'5cem, as iln eX!l!:mpl~ .1.·!lI;ct:llI:tt:': or ()l;ber d~etaf'y c$tr~ngiot1s. ~ssll,l!:l111;:d with food Oil: ~MUr. s ed in solution and wharis eli miriated from the S},5tcl11 ptimg.iti1y with urine, TilL s .mJt.:sbi1J~- 1l!rJce :app'[l~ach 13 not fu]ly:;tpprocill.ted 00 date, btu.1t isimpossible I];si:lLIg the S.iggaaitd-AllIdeitsen 0]1' Henderson-Hasselbalch models.

Thisbook .i:[IlCluCie8 the ud;g;inJ~ chgptc;1:t; of Stewatr's cb5:.'li.c n:ei1J[use g:[Id titl';1l:I1IY other COIJI.rtriilYlltnOrIS relative tothe acid-base disaurbances jn differelLlrt clinical w.lLld idons". Itwillbe dear 1[0 the reader how the pJru~ ... sicocheraicalspproach can be ihdpfu~ ill underseanding meclian:isrt'liS

(28)

ba~e~}' underseandable using d':ie tmdjj~~onOlil approach.es. Clinical Olic.i:d.-base eqrnJilnrum has been stl)lcl~oo formQ~ dl~n ~~OOyear.s, Nmhing ~~s d~fu[Jjh::Uvr.;:; however. the ll~~?lijCQC~el11k:al. ~PllW~.c:h ~p![1I;:s~n~5 ~. further step .in thus ~dl~r.co:mpHcate.df.idd -not just to c:otnpu~e the pH butso bettell: understandthe PJdmph~rsjolbgy of t:h..:: Syst:":111.

[1'921-,19'93]

In Memory ,of P,eter' A ,S:te'w,art

lohn A Kelll!!lnll Paul WG IEllllbers

Peter A Stc .. vart \IlaJS born and raised ira Win.n.ipeg, MllJI ieoba, Canada. His undergradu-ate education was at the Univer.$kr of M~ni~oib;lu,·hel:f;; hf;; gj~duj!~t;d ·'J.,·i~hhQn()!rs in 1943, He >Wl> aradar ol'Hce;t in the; C:iln!ldi.;lln Navy d!nri[IJg' \Vwn and! I!lter :ilt:Ei:nd!e;d. the Universiry ofMinnesma wlrere hereceived a MS .~lillphJ.'sk:s and mathematics in ']949 aJlnd aJlPhD in biophysies in 1951. Dr. SteWlli1't \VaS a charter member of (he Bioplty-sica.1 Sod~~}' ~.l1d a Marlde Schola.l: in scsdemdcmedicine,

He beg-an his academic c-areer at the University of [1]]]]018, tint in the Department of PhysioJogy.rhe:.l]j a( dl;e Necropsych i;IJl;ifk [ns~uw~r;: as an A$$~$C1ll!t P'tOf~5rot nf Nr;:Ulroph}'.$iol. ogr. ]n 1954 he: movedto ErulDtr University whe:re: he became an. Associate Professor .ofiPhJ.'siolog}"lPhysk:s and. BJom,etry. \'l;fhiLe on saibbm ical -a:~ ehe Brookhaven National LaborawJrY he became a mo:~ecu~a.b~o~ogJ.sl; ~5 wdt ]:n,dJeed, illJ~he words

of U[lJe: ofhu5 collbguc,,;, Pjerre Galletti, MD, PhD, "he: could! teach aJnyoofiilponerlt of the physH.og)col).rses fo[ medicaland dental students, arid be 1I.1ili effecrive advisOr' for a wide variety of graduate srudenrs, several ofwhom now occupy senior p06.ltl(H1S a~ majOif uniVt;;·r.$I~~es:"

In 19(:',J Peter Stewart joined Brown Unive:rsi!:r as Professor of Medi!Cll] Science, He worked 1'0 develop a curricularn ]n which marhematics, physics, chemistry and biology were tau.~~ as aUluiJied science and Qr;:n~r;:u;:;d Oil! the ar'P:~uc~rioll! ()fma~helnat:i,~~ ~f1d ~.11~.~ydcail nle:~hod$ to tile ttgu~:;l[dDn of phy5idogim~ srsrre:ruTIl>. FItOttrl 1977 to 1983, Dit .. Stew:ilr[ served as Di.ttctoit of the Commonwealth Fund Interface Program where generations of students were taught how to blend scholarly discip]]rte wit;h humaeitarian pursuits.

Upon his retirement, tof,lCi:thu with his wi fe and fellow sciencist, Baberte Sttnw rtt, !I. prize; "vas estsblished !by thelPto,g:rnrn io Liberal Med.h::aJ] Edr»caJt:ion to honor the students who best

1[2!EiJ

e:rem~jlif~' t:lhe values they peomoeed thrm.lJ~h their O'\1,1'n dedieaeion eoa seieeee-based liberal ~dl,l~~iQn,

Pete:!:' Sre"",",ft ser ... ed JS J W[lsu~Jtafit to the HtlmJ:n FactDJfSG:roup ·o[ dte Lockheed. A~.itc["di Corporsrion, and. was for many years a member of the NIH Committee for the Medical Scientist 'Jl"~in~ng P1:ugr:atn ~nd;;J,L$O a h1~nrl;b~r ohhe N~t:io[l~~ Instirure ofr'Ge[let"J M",eclk~~ Sc:iem;::e,$ Research Career A"w:rd Commkree,

Dr. Stewa:rt's ineerese in Acid-base Physiology grew out ·ofh]s comm~~mei]JrJ to ·~ea.ching and his 1,lI:l~.I~ed. ~pp[1Q;lJ;;h W ~i~t'1Qe" In. ·.~.981, h~~$ bndm~:~k boo].: on "How tO~:[Ider·$ta(](j a.dd.':b~$e physiology,." "."ms published !by Elsevier, He would have been pleased to knowthar .k,"l [I[].]l o[igi.~ nal wm:e:nts a re nocwp .. rt ofthe book yotlare readlng,

In 1983, Peter S~~\v~If~ re~u~d to Or~$ Isl~nd .in th~ S[r:airt of Juan de F~c:~ n~ar Se;I~tle, Wg~hingron, USA, H..:: suffered from heart [:lIi~utt; andve[lJtri.cub:r arrhyrhmlss l:mtn.o:[I":: d1":: less devoted his reairemenryearsto public service. Hewas .. fotlndi:[lg~lfUstee of the Eastseund Public Library on. 01'C11S Island and wasalso a member ofthe Coumy Warer. Advisory C0f11ll.1il1-

A~thongh passionate lJil. his dt]Jl commitment toexcellence in science ":[ld in !l::o:mmunitr endeavors, Peter Stewart' is best rememberedby his colleagues a:l:l.d fr]ends for his ready smile, gentle il1anoer. musical tjlle[lrts,i[lfQ!l':m~tl s~y~eal)dll,l!nfail~[Ig S~t1.$~ oJhillmQ!~, H~enddl~d~he Iives of those around himwkh his enasistenr clacerfulness andeternal opElmisln.

He wi]] be oo.rcly missed, bfll!l~ his wo.rk n1:ay ]'1-0\1,7 live on.

[PART I]

"'How TO IUNDERSTAND ACI:D-BASE, A Q!UANT'ITATI:VE: ACID,-IB'AS,E IPRI:ME:R F'!O!R BI:OLOGrV AND, MED,ICINE"; STEWAIRT'~S CLASS,IC: TEXT

[INT'IRO!DU'CTION]

Peter ,A, Ste'wart it

Add-base chemlstryisan ifiilpO.if~<l[lt tlYpic in biologr.lbl.oche:mistqr,iJh~r~~.o.l~"3Ir" 11I:nd clinieal medicine, a topic that shou]d bethoroughly understced by everyone in these fields, Despite this iIIlpol:'~~l1Jce. the tO~'1icus us,u~I~~r :appms;ched .il1Js piecemeal. qu~Ji~~t:ivt;, and conJUs.ing way, so '[hat hlis:und!e;tstan,d!:ung :a:rt.ldi. diisagti:;"::lll~rt.lt seem tD be; muehnoore C~ln(llllon than the" ind ~lrr us .. diml q~:a:rt.ldl:;,ttiv~ unde;tstand!ing that is needed, Theseason js pan~y that ;,tddt·ibas..:: ch~mht:t)', like ma:ny topics ~.Il.Ib.Uo~.og}rarJd. medicine, !C<l:[I. only be simplified downto 111 certain minimem level before seriouserrorsand misinterpretations result, This minimum levelisthe elemeerary physrca.l CI1~111is~~y of a,qrl,lwus soludons conl~Utdng ions, ]:~S IlllljlO!l: t.nesssg~is dllI~ we can only make sense of :a.ddi.~lbas..:: bdla.vlot of lboo~' tluidisibr takung in~D account how all the i.o.liIs,IiIH[ justhydi.w~..,erJ.non;s" [J:a[t~.dp:abe :i[l~h11lt be.]]<l,\I.not;. hyd~-'t:nnolnS ~[lbodiyfllJ.idscarJ.rJ.ot be uederstood. as indepeedeaeentitiee, Ttea~]ng tha~ elementary chemistry qJUantitati.ve:IJY. aswe shall do in this book, not only enables us to understand hydl:'ogeniOI1J hel1~vror d.eady,ut ~lsol:'el~tes that behavior to fluid! and electrolyte lbabnc:..:: .i:rt.I. t:I1..:: whol~ ot:g';ll.nbm .i:rt.I. a d~:tt:ct and cohe:~rt.lt: '\Aray: Masi:e:fi:[lg~he elementary chem.ish:yi~ therefore wen worth the minor effortirrvoleed.

W~ ~'li[~.$r;nt th~ lnin~tm,l!:m 11J~~,$~~:F~r phY's!~~1 ~.nd ·chemjc~l pd(]:t;ip~~s in. Ch~['J~r;r 2, Thr;f~sl; of dl": book will tlren dJW10tiiS[t:at~ their relevance :a:rt.ldI. powet lbyexplaini:n:g: tlh..: appattm compkJ.litie:s of acid-basephenomenain simple but rthofOillglh and qnamjt11ld\le~ern'l3" The treatment will progress from the :sin1l'JeM system, pUire\V"llJter. in Chapter 3,. d~rough progressively raore m.iTIpl,ex solutions and body fluids .in succeeding dlap~I:'.$, to the!Jnal. SUTriSIngly simple~~;lJta menc arr wlld,~.b~Jdy acid-base balance in Chapter 9 .

. MOOenl chemistry; even atthe elenle:l'lr.-"rr levelneeded w under:S~<1Ind hydrogen ion behavlor.,ushl!gdy ul1Jd,er.sooodun qu~.ndl";IJtive, and therefore msthemstical, terms, Ul1dl~nii;~y, th;,ttn(la[}let.in.'.lltic,'S has lbee[l. avoided .i:[I. acid-base ehemistry for the sensible :~~'Sol1[hat.k was notv;erj! fi'i.Ucb help before OOfi'ilpme::rs ]becali1.eav:a~.halble, I-]~rdiru.se:n ion. corJce:[I,tf:::HiorJ.~];,e focus ofscid-base ,dlienlis~ry, d.epe:ll:d.s Oft severable variables, <1Iflid. the qual:l:~ixatirve de:scr~)~ion of its bd.lavuol:' .rr.;qil)l.~.F,eS lIla!]")! simultaeeoas et:)II,l!;lJJ;lon5 .•. R":]ilkh anal.ytka.~ 's.oludol];s fOI: 'such sets of c:quations ... 1lI'I]~n the}' canbe wttit:rr..:n at :al~,. are not l:I. ... ua11r oogatd!..:di as usefulbecause they ;,tt~ so. 'It:nw~.elJdy fot pt1lictica~ Cltl.cuht~rJ;s. Computers .• i:IlliC~llJd:irJ.S' handhekl pwg;ru:mm11lb~.e calcula-

1[30]

(Pl'lRT ]- lHiow TO 11JI~ID\BRSTAIl[l Acm-BA:sE, $TEWAR.ir'S, CLASSJ£ liEn]

rors, have co.IIlple~ely clutl:ged~hi,s situation; ]]Un1e~:iCl1~ values :for~he ,sob~om (:0 such equadons ~:~ nO\M eas~.~.y ar.ld~Jiud~y oibt~uned by CQmputet:-:uinr~~m~l]ted t~'C&!Jn~glues of oumeeical ~nalysi~$, As a .~~('lU~i[:,OQ'.l11p~il;e'f.$ :&!Jav~fr.;v·Q~utkm.i:z"d. Qu:rib~.Hl;y to ~;r.laUF~,U!tld~~.s~~.t1d, alJld ptedkt t&!Jc:: acid-base behavior of bodyflll:l:~ds,. 'O![ any solutions ofbiologk:'ill ~1[ Medical interest. 1'11.1s book is both an e:>.:po~;itionj, aJ:ndan e:-Kplokanion for its pitacd.uJ usefulness of that revo]uuon,

The trearment of gdd-basechchCI~suy mid.bio~ngy in.. t:hus!J.ocik blilC::O:ss:ild]y[lH[ at g.1l ] ikc:: the treaemenrs :1'-11. current textbooks and reseaech l\ou.[[JakRdere:n()e~ to previous litetaJmrea.te tfuerefore sparse, There are so ll.Mltlr differences in d.e~a:il betweenthe qmu'ltita~ive analy~ical ~[~a~:t111;:1JIIt presented her-;e ar.ld the c.'OnvUldonall. qua.1i~s.tUVt;~r.eat~llents that cmllp~:~i5Qr.lswith even g few of the c:~J;!>l>iall desctiptions would have grc>ltlyuncte:ilsed file size u[[his book, It seemed. more vsluable 1:'-11. this jntrodl]CU'lty aJ!1:!1:(flLn~to !1:O'-1lce:nt:lf:ate on thebasic principles, J:nd tfueir .import'ltu:~ quan~i:~ati.,"e.con8eqJUence8> le.llyiflgw the readerthetask ofcot11:paJr]sotl and ~[~IJI;$lat~QIJI.

Thenonmasbemsdcally oriented teade[[J)u.o/ask atthis po.i:'-1It. 11,o;:w' meeh of this m:wCi,~a:'-1Itit1l:~ive undersesnding of acid-base can be achievedwithout a.c~u!'llU}' working through all the ocdiQlIls d,et";li~s of t&!J~I:n.atbem~tks and the wmputt;~ 1:lf"(_15:~m5?The answe~ 5Ul:lP~jt;d b~r dlis book isthat the mjnirnum .. level of mathemarical SQphisil:kgJtiu[I .. tequi red is only dl:at needed m aJpp.[,eda~e what the relevant equations mean, why~hey mt]S.t be true, tmd. haw~hey are relsted tD each other, Hewthey aretobe solvedcanthenbetreated as an incidentaltechuieal problem. Most Qf~hem~tll,,~llatjcail d,et:a:u~s the~fu~ ~~')pear in apper.ldic:e$ to the ~~')pj~D'lldj[~edl~]:lt~l:'.s rarher t:&!J:iln In the main text, They are there ffJ.r those wllio"vg:[It: them, !bJi.]J![otEho&!:;who do not, theywim not interrupt the IRa"" ofthe mJ;~n a[gt]mems"Wha;t"11e \vaD)! to knowis wha~~b.e lllll:~he.l1lJiat.i.cs tens us about the behavio.r of a]l~he variables in body fluids. especially hydrogen ~(lir.lQQ1.10~nti"iiOI1J. (lir.l(';~' we h~"lt; cspec~~~,ed th~ gu~ndta~ilve oonst[,~ilJlii;S on ii;hjl~ b~hav~Qr thstthe h,vs of phirs:ucs :illi.dch~mu5uT require, O[lcc: c:illcuhtcdby thc Cf)l:nput~t,[h:ilJt he&!Jgv:nol[ btt"L.adiily l:I;n.dcr5t'Ood trUhCIQOi.ll1PiJ]JOCr-'gc:,rtet:iltro graphs and tables of wlJi.]c:-;, Th~sep'wvidc gualitatuve as well as quantitative pictures of theacid-bsse behavior of ,eJdl solution,

In ;5:mum:il.I:}" this book presents :iI.lilonJJtmduHo;[1al trceement of gdd-b!il.,>e behaviorjn !body [t]ids". Its purposeis to help the reader \'(I\otl;. tllrcm,gh the den1en~aJrT ph}'sJcaJ c!:1.emisu), of .io.'-1Ilc so~m.i.ons eoehesynehesis of a cle~1JJt'> quamf~at.i.ve> ancl.p'r:ac~]cal une]ers.'~ant]]ng of bow a:i'Jid.w'hy hydrogen ion conceneration behaves as irdoes w. ehese solutionsand in the whale o.rgalliru1lll,

[CHAp:TER :1] Body Fluidlls

Peter .A. Siewart 'f"

Thetreatmenc in th~ followung F~g.e5W.m. focills on ~f;idl':~a5.e br;h!lv~m in theflukts of the human body,. ibul[ it shmJ.U he, dC:!1r thgt the, tl1e,thodl and [he,r.e,sI[]~l[s are, e;,lsi.ly c:xtelJJJdod to a:niy and 11IH biological s:itu11lt~o!l1S .i:'-I. wh:ich acid-base pheno.me:na.arei~~po:rtara)t, The properties of humanbody fluidsare of obvious clinical imporeaeee, and therefore provide a highly motivaeing!ll.5 well ~5 s1:;~diic ~ndconctl::terd~n;n~ fur OUX' ·!lI.na~yses,

TIle hll[Iru:n !body is'-IOlf[Ir111l11y about 6i1J1fo 'iJ.":a!te[., In 111 standard iO-lq~~ male :adu]~. therefore, there musebe about 42 ]]te:rn of l1IqueOfllcS selutione whore acid-basepropersiea we needto unde~sil;a(]d. 'Jh!ll.t tne~[Is u(]d~1:5rt"ndling why dl~ hydrQg.enbn oonil;l~~nil;rlI~jon h!l!;i the WI!.~I,l~S it OOC:S in I:IIC."C fluid!s and how arid why k chllrtgcs 11$ l[ dDCS, \eVe shllm hc:gin to do that jnthcnest clnpte[, . First, in this chapter we pjjesema. Smlilifi'la:r}, picmre ofthose 42 liters of soh.ltnons.,

Thr;~ody isnot, O'f' couese, sump~y a 42;.U~t;r ~[Ik. I~ is org;m:uz,edlinro Ol:gans, d5SU!~5, and cells, so that there a:~ In,my diffc:'~lJJJt .litHe solutioas, and we tnightc%pect eech Gfthem to h:l.lve its o.wn peculiaracid-bssebehevioe, Fortunasely, we lirad~ha~ they ITIll,ybe 1I:Lmpedtogedlef ooW:'leni.e.m]r inm a SurP.riSillgly smm]l nnn1ber of .represel:llM]'ye solutions, sothara cS1lJisiac~:orr an~&~?5US of"~ody·~u~d acid-base b.eha'i.rUO!lfis indeed Iltact:icalTwo o'~~OU5 ~l]jIjiOr s~bdhri8~.on$ of the 42 litess are; the intracelluler solutlon, abcJI[]t 15~itc:t"S" and [he .eK[rncc~llub:r soUU!tiort, lIbol]Jt rr ]Ute:rs

In~hr;body, 'soludoft$ '!lUC.~ 's~p!lUl!Jl;ed fmm Ot'l~ another b~T jllell1bj$n~s. ~[Id the prcOr<el:d~s of thc:se l11emb.b:>I:IJJJC:S can 1I.~SO beexpected to ,,{fcct add-ba:."cbeha!.vlot lbrClommlHn.g thc:: kjnds of .i:meli':ltctnons t~at !C:a:'-I. occur her-ween the ;5.o.IIllJti.o'-ls, tha~~hey sepat1JJte,\¥e shall thereforefisst developrheeheory andteehniqnes neededeouadersrand the behavior of solueions m. isolaeion (Chap~~rs 2 thriJU!gh 7J '~efr'o!~ I;Ulmung to !the CCl'l11k;~k';Idol1is introduced b~r these tllel1~hltmeS (Chapter 8). Wc shall thelIl be"vc;I.~. prepi1lrcdJ~o undl.erstaod aeid-basephcnomenajnthc whole body, so-called '<lldd."':b:ase balance," andirs regubtr.on by the In:ngs 11Ind kid:'-Ie}'!'S (Ch.apt:el" 9).

1(32)

1. 2INifRAi(';ElI.lI.l)ILAR :SOLlJi'liIQINS

T110l[]gh intracellular so]mDo!ns form the large:St gMtC-g:<lte: fluid compatmlcnlt in the: !body,. t~ey OCCHt as at least InlA~inysepa[:He .i:[ldiV'udJtla~. so]ntlems., one inside each cell. Because dufffi"etent cell types are chem.i.ca]1Jy d]Hel:jen~" there is ]]0 reason toexpect their ineernal so]ut~.ons, eo be id,el1lltk;ll [;111, fact, we k:l1lOw dl;llt they a~ie not, .Fo~"t~,u]atdy,~hr.;~1ail1 sh!li:~ a f,e>M C:'OIn:mO!1 dHffercnces ftO:iJm exrraeellulsn solurjons, mJ:d ilt isreally on. til is basis t&ugil: we: jl[]sHfykllnp~ng them all together a:si:[ltf:acdht.dar at] id, fntracellular 30h.H,nonsa.reaJ'W:ll,}'S ]]Iu,gh in potassium a:[ld magn.esium ions and ]mv in sodium an.d chloride, eseracellular selutions are jusethe reverse. Ineraeel- 11l;ila~ OOIIl;id'OIJIS c.'OlJItlll.]n h~gh ~Qn~ntf'!l!tio118 of 'Org!ll.n~~ ~dds.; ?x~:I:;I.c:dhl!.~!Ii:~ sO:~i[]dQ[Jjs a~i1l'Ost tl~r;~ do.

We shall t:hereforeilnd it useful (:.0 discuss an idealised inrracellularfluidwhcse chemica] ~O!mp08~t~on ~,$ Oi[]r best esdmMe 'Ofwh!li.t we"'lould&u~"r; if we CI(Ji[]Hput all '~{Jl4 of t&uo'se~.iny dmps of ttglirltuGdh]hr fluid,,, tl'Jgl::'ther.'\!(Ie: shalluse [OF as the srmlbolmolt this [lI[]H [rl view oluts id!ea] or 'td.rtl]J] [lattue, mnrr:uedcaJ '~m]nes fOlfi,ts composicion ml]S~ :a1"lllJ!}"s be understood to be rep[\ese.mat~.ve tllJtheJf I:ha:[I sukd'y factual, ,except in theserare casesin wMch sped fie chemical measuremeees hlllve somehewbeen made, To keep ~:his representstive qua~it:y .onC]::; alway.s 1111. sJgh!:.'J,.-e sh!liU refer to ~t f'l'l;qi[]r;tTtly as "llt!;IJld!liffi'" ICE

1.3 lI!Nna:SD'UAIi. :SOl!UTIQNS (liISSUE Fiwms)

Extrncdlular fluids lll'ill)' be: subdjvided intoi:[ltl::'rsdtig~ solm[,oml or tissue fluids, blood plasma, J:nd! "o~h,en.,"Wesh.al] devo~e a bdef 3ectOCln h,ereto. e.ach cne, T11e huges~lby £at (13,.5 .~i.t:e:rs) is the .i:l'lle:.rs(~( ial fluicl~ha(: bathes most ofthe cells inthe body and OOI:lM]~U~es· ehe "inrernal el1V~l'Qnlne[Ue' "v&uoser-egi[].~!liido[Jj.bf 8eve~1 QI~ns of the body g~ve,s flS? to ~he l:lhysiologi5ts' ~OiO:cep[ of'homeosrasis, Its rnajer chelnk<l~ features ate: low pOl::a.ssium g:rld. magm:.,osiuln 10[1 !lJQI.nce[)~tl)J!ti.o:ns.,hi,gh sod.i~]:m and chloride !LO:[llLent:r:a.t~on.s.a[)d! verT .Iow 0:1:' [).egli,g~b]eGQI.nce[)~tllJti . ens D.fpr.o~eitlS or other org~nic acids,

:Uke: inrracellnlar fluid, .i:rlJtcrst~t~<I~ HuiJ OCCUI:S in i[][]llmCrnHe: d[)[ypoclice:ts of suklJtinn. irl t&ue: ~[ltersd~es, of Jll bod'r tissues, These are mostly In the form of verythin ]a~~ets., an. tile order of '1 l.t~hiC:[1;: or less, and virtually impossible to sample for chemical ana]]~{s~s. Each one is somewhat dlfliht;n~ frf)mliJ;,snejghbo~5 .. a~t&uoughprob~bly not as differ~(]!: as the OOfn;51JQ11dhlgUrHm.ceJ~ Ilulg.t &;lllnpb. would be, ·W.I}:.lI:t~n::: meanby i:nltcrstiJtig.l. fluid is the "vill0lc 135 liters of sO~I[]t:bfi. wewould ha,ve if we «mlld somehowlnscanraneouslyremove J]J~hose litdepoclsecs from. the tissues, mix them. together, and store themat 37 °Cels~.us under JPp[op.[~abe PJr~h] presstl,res of .oxygtn and carhondioside, It: isthereforean icliea] orviruial flaid also, We shall use (:he srmbo1 ISF fOI~ ~It !Ii.ndtref,el: to k often !liS "stjllJldard'" ISF OO~I'l1ind us that i~toous fr.;pl:ce$e1'I~rll.dVi;l:'athr;r l:&ug:[I. "~[Cg.I."

A '~pedal subset of ISF is thr.;lymphgtkfh,lld. ()If lylIlph, P&uy\iio]ogk",~~'. lyinlJll J:;al1l· be t&uOUghl of asahe overflow fluid 6:"Ql:!il the t~,$s~.es,.r;nr.OUtr;b;l.d( to~heMoodsJJ;l:'eam by ~y of l:&ue:lymphJtk vessels, ~]t arises because :rc:gibsol[pdu[I of fluid at the venous ends .of capillgrio;

BiIOQdl

Pil:!'l~m~ .... ~ 3,,01

Red Blood

Ceilis """"i ........ 2',01

(33)

.... Other IFlluids 00,,5 II

II

~Intel[dlia~ Of li~::Oil.!e Flui~

11:l:511

Intra~IIUllat Flui'd:s ,2:31

(* 2 1IIIiII RBCiS)

Celli lMem'b:ralnes,

IFiiglillilel.,l., [)~<:Igr;:lmma~lc replfe:&ental~lI;ilrn of majOIf body fluid vO~lllImesalmd Irelal~lo:rnslh~IP:S in al stendard 70-lkg humen bodiy. Totall body warlter = 23 + 13.5 11- :;I 11- 2 11- 0,5 = 42 !Liters.

~l1Q:mpl'l;dse~r bd;l:[lces ~ik[adon QlI,l!ta~ the a~:te~ial ends, ~nd also because of leakage ·of p~50· td[l. Dl]Jt ~_lf th~: GIlpmati.es, 'These pjjotd[l&, :alu[lg w.kh. th~: excess fluid, ate cOl]stantly tc111o'lOO fromthetiasuesand remmed tothe d.[ct]bdr.ag Hood pl.asll1ll, as lymph"Beci!!tlse lymph ~:S :~n vessels, .it is possible to sample it, so t:h1U measurements oflymph composition. mle Ofl'efil cieed as appmxui1l!I~UOn$ of the C'Ohlposution of ISF. In . .h1O-$~ cases, dle}' are ~I~~hat we h~l'le, but they 111;l1-)' berather pmJlt approK i hlatio:[Is,

1.4 BILOoOD PLASMA.

The~hjro.~a.q;estHll:h:i1. en~hy in. the bodr Is b]oocil pbs:maJ. II: is a single :Hn:nd, confined to the interior of the eardiovascular syseem, so it~ is not such 11:11 idealized or "lumped" fluid as ISF and. [Cr. ].::i;'l ~rtai:r.l~1 the h1Q~t f~I:~;c~IUI.e[ldr ~.naJyze.d ~u~d in aIlQfr"b~.o:bgy ~[ld. nwdlk:il]e, 'boeccause sam~llesan; 50 easy to obtain by simple venipl;mCIUf~.

Plasma.volume is about 4% ofbodyweighr; or 3 liters. Seventy pe:rce:l'lt.of ]t. abo~!!Jl~ Z liters, is l]o~h1any oon~~ined .il]. the veins, I~ d~"CII,l!~!I!jte$r1lp~dly thtl)llghol;Wt the body am;! is .i[l dfe'Cdvl; diffusilllil ~CUuHihitiurnl wifh the [SF fot luGs!: Slo~utes ~xc~pt macromolecules, Plasma t:hetcfute d~.ffelfS in composidon [[\1:),1:11 ISF n11LJn~.y ~.I:'I h~ protein oor.aJte.[lI:, and this diffe.rer.a,ce has some acid-base con;Set;[uer.aiLes.

In the !body, plasma has 1I.~grblC C![l[lJtC[lt of suspended red blood cells, n~Y[h1,dUr 40!:'D 45% of the tDtaJI blood vol:lme. The prese.[liLe: ohhese suspended cells hasto be~ake.[I i:mo account \Vhen.ana~Y<ling thebehavios ofp11'l,sln1'l"and oonlpJ]~llites~hllit analysis soo'le\vihat We shall

[1Pl'iRT ]- lHiow TO 11JI~IDiElII:STAMD A.cm-EiAsE, :STEWART'S. CLI'I:SSJ)( TEXT]

t:fuereJo!e analyze blood. I.:)lasrna~w](;e. Jirs( ill isolation, w[~hom: blood cells, ii'll Chapter 7. a:l'lld. d1~11,. wlch its normal CQml}letn~1T~ of~:d 'MoodceUs, as whol.e blood, .in. Ch~~}re[ S. ]:~us usef~.~,. ~[I. this CO[lrext, m th~l]k of bloodpbs:t11!il $S ~heintl;~~ud~~ ~.l,l~d of ~. Y~il:y sp~d~~ (~k~ll;ilid)~iss~, n'iltne:~r,. whu]e: UmxlL

T111;SC:1teg:otT .i:[ldudes ll, v:;u:Jet:y of smw] 1 'V"'(I]nmes of special, usual.ly TIlJrthe:r small. JJ:[ld.l,oCJJ]ized, eolurions such llsa~uoow; humor, synovial and. burs-al floods" bile, saliva, and many others. These ~:re sometimes :r~[I;~ri;.d to as "'I;"ansc~Ul,llllil:j; :fllIl~ds, E!ilch O[l~ ~s ex~1~11le~y ~tn['H)fii;·antun ks awn lacg:~ situation, lbl[]t the:y are not ofinm:h qml:[It~tllti.'1lC s:~grtiHGlrtGe f,{}['(l,<1Ilole:,_bodly gdd~ base behavior because they onlyjotsl llbO'l.lJt {J.e:; Liter O,I.l theaverage,

TVi'O of ii;becSe '$[:I.edaJI.fl~:uds, hO\Vl;Vl;:~> are of ·!ilddl·:b~s.e ijll.pO~I:U.t1C~> .~stI'ic"~d,dJ':' ~;[Id pan~ eresric secrerloe. Gastric acid Girt be 118 lUUCh. 115 OJ. NHCI, and pg:[ICOCgJtIc 'JlilAice::'" contains biJ#l concencrations of sodiambua almost .M cMor.udc::, We. shall.examine ~[I alJJP~ers 411n.d () how such. sdmions, canbe produced from (a]b~ii:le) b[oot]p.blSalll and. howthey ]ntern.c~ inthe d.1,1Od~[U~:t11, Oth.erwise, W~ sh~ll~1ceI'l'l!nyigif]ol:r::: dle ·'oth~iI:'j· body ~.l,ljds,

The vU:~I[]111e5> ll1embr.~1iIe:8 sep(3f:aEing, ;,tll.d lopd.ogi.cg.1 :rd.'ilEi!:JliIships 'be['(IiI'Le:;[1 the tngiUI: bod~' Auids. just discussed JJ:I'e summarized dliagrammllltl!LllUy .i:ilI. ];:ign.re 1.1. AI.! these solutionsare ge.nerallr considesedto be in osmcticequilibrlnm because JJ]l the. membranes are freely pe.mil.eabae eo 'W1l~er. Booy-f:Iuid osmolarityis nmmaU)T maineained br the hrpmhalamus~piwit:a!1·:':bd.!:ley team at a vaJIue close to 0.,2:85 {}stnoUr:::/l.itl;f..

The solutions ]nvol¥ed in majo:riOOdyf:lrrl.i.tffi are (70 kg man);

'.1. l[lt:mcdl[l.lgr Fluid (Ier): 25litcts; The sum of all the 50]uEbnsililsjdc lIUrrhc cells of the: bod}r.

2, Int:e~~u~i~~ ~F~l,lid (1:Sp)~ ·t15~k~il:3; The sum of aH~he~lul.e POc::k.et5 of dS$~e :Auld .In. the i:me::rn[icesbet.wttlil. 0:115 t:h.ral[]ghul[]t the::bodly.

3.B]ood Plasma: 3 liters; 'The inrersnrial fluid! ofbleod. 4 .. Other Flnlds; 0..5 Liter,

Total Body W~il;er ;;;; 42:1~t.eI's ;;;;25 + 13,5 + :;. + 0.5 lure~,

[CHAp:TER ,2]

Go,alls, De'finli,ti,onlS and Balsic: Prfnclples

Pete r .A. Slew a rt it

Hydmg.en ~on ii:;O[lCen~ll';I.idOI1J ~n bodyfllmid;sis eXl;r:;el:nely.loi!J;-. on d1J~ o:rd£;. of 01[1[; ten-milli,{l\[ldl to one hutrldl:'i:d·'ll1i.m.O:[lt~ of an ~:qlliv:al~;[lt per Liter, \Vby arewe So interested i[l the behavior ,of such a rare species? One reasonis i:h.at as P[otf'f.'IIS" hyd.mge:n ionsare very small, and. t~e:refQ!re have a yeqT high charge densit:y. This inturn results in very largede'Ctrk fildd gr;ld~e[l'1;Sun~hdr neigh'bQ[~CH)ds, The}! Inay t:~er.efQ!r.e have ~In['l'ot'tanu eff"ct1l (}[I other' molecules in. t~~: su]miml ",,-toll:nd. them, even at very lmv '[o:nce;l1[t!lJtifJ:!li5", :]n pattkIJ.d1l!:r, hyd:ttf)!,Ie!li bon.ds, 11!ft i.l:I1pott11!:ii~ inthe detefl:l1in11!tlo[i Orm11!cro:fi'lo~.ecIJ]a:f structure 11!ndGonfilgurnt:non"n:nd the.ir stl,engd'ls should bep:itrt:.iicuidy sensieiveeo local h~X1:rogei11 ion (;oa(;e:l1li~r:a:~io1l.s,1F'~r~~f. [OE these reasol1Js:, enzpli]r;:s;ctivutUr;:s. aee Qf~r;:n s.igni.:I!ic!I!.ndr de~]r;:l)ldr;:nt Qn~oc~l '~ydr(lgen ~O[lCOI1J~ centmtion.

Changes, ill hydrogen ]00 concentration may also have important effects 0]] biochemical ~acdol)r';lre$ S~m~l~)r because h}'dfog.enD01'lSaf~ iruvdve,dl in so ~11alJl}' biQdleill~'ca~ n;~iC[iQflS, Thus rum~tipkinvol'!,''l:me;nt also {]0!l1[:tt'lbute5 tD the comp.b,i~ie5 ofunde;tstmndung the dynamic:s of hyd:rogen ion oom:e[it:ratlon changes [Ill particulss, bydroge:nkmsc11!:n be formed from ""rater or can be de8trn~~ed by the fOirmatio]] of '\l,m~:er. Becsnsewaeer is by orders of magnitudethe most cf):l1Jcenu:r';ltOO substsnee ~.I) .L1v~[Ig SyS~t;~ll;S (553 M). it p~ovidr.;5 a[lefr'eCdvl;l}'il)ex~ausdbl.e OOIl,l!I:Ce"" or unfull~ble csi[l.k, f'Or hyd~oge[lions ~5 '~-e~~ as for h}'dm'xylk~l),s, These two ~OIJlS theee{bite:: bc~g.v.e;q.l(]jtc d.iff~:tt.rt[ly £[Oru.1 ~J'[hCl: 'ki:nd'l Qfl(J;['J'~ [~OIJt donot have suehrescutces evailable tothem,

ClinicaUy,&Uydmge;n ion cO:IJJil:~;n[rndnn, ~lH~]},in !body fluids isimpotmnlt !IS !I. u..~fl(]~undi[,..~ tor of several. differentkinde of p11!tilolog}', I[H~I is mO!5:~ easi~y measured in blood, v.i:a, al small 'l,!'tlijipt~:i'J:cmre s:amplle and a pH mete:1f" The I[FJ+'I of almhiiecl,,!eD.oI.'IS b]oocl Sij,mpLeb fi]silu]LY[iea:f 4,5 x 'UP Eq/Liter (pH 735), wh:iill.e a_nej']a]b~ooo I[I1:+JI is near 4,OK HP Eq/Leer (pH 7,40), V~lll,l!r;:s. !l!llmve about 1.2 x 1'll~Bq/Lutel:' (pH 6.9) or below ~IOOll,l!iI;L6 x '~(Jr~ Eq/Lull;r (pI'-] 7,8) indicate;~ifc;"[~l:CJtcn.i:!lig sltustions and demand i.mme;cli'Atc~rt[~t"!lC!lidO:!li. Betweenthese Iimits, wide Vn.t.l:HDOlnSc11!:n occur, sometimes ve1fl"f::tpid~y. It is irn'ilpo:1f~11!:rr~ tD understaed how slJch

1[36]

vll.riations ~rise. how blood [H'] is rebted to [H'-'] ]n other body fluids, 'and how thebody may be helped tor~sror~nO!l:mrll,~ oof:id~dolJi$~.

Th,:ge:net8Jl goal of thUs book is ~iUai:'ildt:;ttive a:p~Mation a:[idl, u[idet3t:1indl,rng of]]}~d:fogern ion ~oncentmtionand irs cl:i<ll]~:S in a]]y hio,~og.i,~~] soh,u~on, QUllntitatiIve uro:De!s~~nd]ng req~]:res precise lmowl,ed~ of dl~ s~.glJii ~i,C'alJii[: 'il'rllrlrlllblr.;s in the S}"5rei.ll and the p:hyskaHy n~C'e,SSrllry q~alJiil;i~ tlth .. 'C ttJ1Itbnship"ktwttn, them. Out specific g01l1may thctefnre be stated iii] these t:c;ifncJis::

In a:I:lY given solueion, und,er ~ny speci lied condieions .we want to establish (i1e quantitarive ft:!~a~iolJi$h Ip.sbe[lJ,."i;en h~ill:-ogr.;11 ion oolJiii:;er.l!;r:at~olJi ~:1Ji. that solution rllnd rlll~ the other vuhib~~sun I:Ile: so.~r[]i:io:n~h1lt: detertninc il:h;,tt hyrliifOf,I'e[l iOo:[I, 'OO:r1ceotrndon.Wc sh1lm then, be able iI:O underM:1irn,d!,,:tnd!eNplllJin, the value of the hydI'C\"t:n~on coecentration interms of those deeermining variables,

,Atl11ed with this qrumtiJt;,tti'!,.'C understanding, ,vc; s.&u1ln be able to an5"wl:rplt1::dsC:~' and confildI.e,[idYany q~ue3tiO[iS abo'Llt buw arnd,,\11Y tbe 11yd!roge[i Jon ,col.ncentt;;)Jt:lOI.n changes as .it: does, ~i!:ld to design !l1itj.on~l and effe~tive the.ra:py. on. :it~ua:l1iti.t~:tive basis. for situations ]oYoJ.v]ng rllbnOI111all. [H+] vah;i1.es (a,dd.':b,acsr.; d~sor-d)r.;:t:li).

'Ioachieve rhlsgoal, we must fiest spend some timeand effort to Mllike sure dlat we agree 00 defin]~ion$atld~hen, ]:l1i.~he resr of this chapter, forluub~:e cle~rlly~he basicphysical and chemkrlll pri:lJid~'l~es ~hat'ill,dll beour tmjor roots fo[ analysIs and guantitrllllveU!t1d~l'S~andll1!g of ~l}.,jiiJ(JgL;n ion bd1:avio.r in body fluids.

2 .. 2 IDII!iFINI1iIONS:~: NllITRAIb., :A.c:lIi)IC,ALKAUN~A':::IID" BASI!

The con.ccFt fir an gdd or 11 base .&u!lS g.~ntll:g folk ~1.L s tDrr, but arather s:.&ufiifl: scientitic hustnry, <lind! emotional afgumen:ts ha,ve ol)re[icen~eredl. on the .I:Ilea[i:~[ig3 of thesewords. For the PUr-POISes of d:'l]siwo.k, we shall adopr tile vei!::}T simple bue pm~:~ica~ ~:l1id useful defi]'li~ions given below, Thr;ya~ veLy cbse tocurrem CI()~lHnOt1 U5rllge ~:IJi biology ~.nd h1~d~,dn~. and they w.Ull seeve vl;ry wdl out go.a~. of 'r[]:[ld~rgl:!I:[ldi[lg qrumtk;,tli:ivdy howbnologi.ca~ 1Icrd··!b!l£i: ~"r5:teInS behave,

IDe:fi!!l:i:tion: a solution is said. t:o beacid-base nemral if its luyclrog,en ion eoecentration is ~gual to ItS; hydroxylkm ·g011Gt;lJitl:'ll.tUQ11.

A.c.i.d....:IJ,a,se :ne'IJ~!l1i]i~}' isa very special, m!lely achieved condition, It musrbe Cllrefu]ly distingulshr.;.;I fwm d~c:tlt'krlll [IeutnI,lHty, a wit'} dHlfer~lJit, af:id oo~Ilpletdy gel:ler1l1, reqijiUlt'el11e1:l1t tha~ aii sO~r[]ti()m [[11t..,1: ,,"tisfy (Sectiun 1.,4,),

IDefin:i:tio!!l: :it solution is said. to be acidic, or acid, if it}sh)drogen ion wn~en~r:atiol:l is greaser thank,,~~ldri}xyli()n ·g011'Gel)~n:lltlot1.

nefiil1itioma, 501ml.On. I;S 5aJd. to bea~b]ijje, Or bask" if ifrs b)rdrogenio!n roncen:t[':;ttJon is less than its hydrox.yl ioaconcentrsrion,

Hyrlitf)f,l'en. iQ:[I.cfXLceo.tt1ltiu[I.b}, il:sdf, is de1lirlY[lf)[ areliable measure of !lddity, 1I~bH[I~ ity:, o[[l:el):tra~.ity,not is its n.ega~ive logaridim, pH .. In pure w:a~et, for example, hydroge:n and

[.37]

hydmsyl ron ccnceerrations alJea~ways equal, so pure w:a:L'er is ah.vaysacidi-base neutral, bur irs hydtog'el1iuon 'ConoenJl;~lldon varies Sig:11JEuc~[Jdy with tetnl'};l;!111!tuft;. from 3.4 x ·~O-~ EC]/Lu~et" (pH 7,5) at 0 ')C~Q itS x lO-? E.qfL~ter (pH 6.1) at 100 ~C. 'Jbe ootnm01'l~extibook s~~.tetl1ent tb:a~ n,!::lJ.]trn.1 it:yis. ",It pH 7.0, C{l[tts]pO:[i)di:[Ig~o l1.yd[;oJi,l'I:nnon colll.c'!::nU1LEi.on of 1.0 x '.~.f.)-7 Eq!Uter.

is on~y nut: in ptl:re warer 1l!t 25 "c, In particnlar, his not rrue 1l!t hody temperaaure, J'f ~C, fur which due pH of pure wa~:er is 6.8.

Dcfilmition: A subsranee is an ",cnd .if~ whea added to >I snliUJtiO[i), it hdlll:gs about gill inerease in the h~i:rdroge:'-!iuoln eenceneration of the so1.uJtkm, il]] .othe:Jf i.ndepe'-!ide'-!it va.thb~.esi~.~heso~'utio.l'l .r.enl!itin:i:l'lg conseaae,

Defsaitioru As.ulbstil:m:e is :a base i.f,whel1l. 1l!ddJed. to a sohnion, .~~ lbt-lngsabouta. decreasein the hyd~ ion concentration of the soJm.:iO.l'l. al] other independent variables ]:l'I. dte wl.u]on renlaUl.mg consranc,

Acidsachieve tbetreffect either by dissociating in solatinn 00 yield 1l!:nani.o'-!i.p~m 1l! h)~dfOgeo ion OJ1'by aS$ocia~i:l'lg with a .hyd.roxy[ ion and. thereby increasing the dissnciation of waeer, Bases act e'~dler by diS:$odat~Qn to fQll':mll cation p~us a ~'1ydm·xyl Ion or by $$sodating with a hydrogen ion, In ,,]1 cases, water dissod.athn cqlJ.]j]i!b:tiuill (Ch:aptl:i: 3) .te"djust.~" with thcfiaalresulr s:pe:d~ fied in the definition ..

These detinitions Inay ~:pI.'lear old·fashlQ:ne.d and velfy s~tnph;:~nli[lde.d, paLtk:U!~~dy~-o the gd'll'.1l:[i)c:odi student of physk",] chemistry, It is rnuchmere fashionahle to fo]low BmlilS[e:d aad delin.e il:[i.:!Lcid as :a PWooil d.O:'-!iD.r 1l!:'-!id. 1l! lb1l!s:t as :a PWooi] 1l!CoLeptef. That term i:nol.og~ is U3efU~ i.n many non-bielogical siruarions.bue ]0 comples solutionsand ]jyil:~ organ:isms, the ddini.ti.o.l'ls given here are much more useful, Umfm.'tUllll~ely, (heprown-diono.r/p'roton-:1lCOe~)lL'er~emlinoJogy has encou~.ged a:[lidenld~iC!lldon of '~add~' wkh '·hyd:togl;nuon,'~· whkhu5 very misleading; It leads ro thecomrnon, g:[Id. cO:[Ifusi:'l:g, gsslJ.]:mprinlil. digit the Q[i)]Y siglll.Hic:ant gSpe:.ct uf·"addi:llI:g add" toa solation isadding h}ra.[Joge:noon:s" Dr i:ha~ :adJdi:[ig h)~i,lrogej] ions is equivaleruto '<:adJd.ing m::id:" ,,\rhicl:-i it is ]]lot, as we shall see in Cha.pte:r 4. Thislniruden~jfi(;Mio.l'l of "m::idi" wirh ~'hyd:togennon"'~,mdelflu~8 much of~he dJ~l;p"[lQQ~ed wnfus~on ~lboU!JI; ·(;:;IJuse~effe:-ct~el:atlQ:nship-s in acid-base Che:l11L~try:. [It also Sug!,fdi[S. that Il}'dlrogelil iU[I. ·coo·[I:mrnJtiO:[I . must be anjndependent vatbthle in solutiens, whe:re:asin fii.c~ h11drogen ion w'-!ice:nmi!i.o.[i. is :alwao/s il d.epe:nde:rH Vl1it]able. Italso hinders us fW.lIl.ealling carbon dioxide all a(idi.wh.ereas in bet: carbon diioxide funcdon'$ as b~r f~.:r~h~ moo~hnpon;a[IIJ; &ung~r;: weak acid in Hv~(]g Sy'SU:II1'S and their environmenrs,

r;brwllll~dy, such bbe.[s are ]]1m :$0 important asehe ]]'IfOm1;~U]On and. underseanding behind them, Wh~JI; ~njltrer-sin.~iO:logy and medicine is what h~[}Pl;I1;S to the hydmgen ion (;Q11(;t;l)t111!a ti.o:[I. ofhllpo:rt>lm s.{l~lJ.]ltiO:[Is, such :iI.'-l Hood ]pbstn>l, ISf', >I:[i)d ICF" ",nd. wl]r;~rhdhe,t 0.1: [lot we ca]] N 1l!~a.lb1l!se, orcarbon d~.«..: He anacid.Jsaot nearly aslmportaru 1l!s .. ,rhdher "lie ca:'-!i. e:;;::pbi:n quami~atiivdy the effec!js on any so]utioo of adJding Na" or CO~. What enables us eo dio that is t10!; rrerm~nO~Qgy but cakul!I~uonsblJ;sr;:d (lin sound physkalandJcbemicallldndples, To ~.ehleve our g.o"'l,. we [Ie:e:d mo d.e'!.'"Cllop the :l;lJ.]k,lby"vibidl such ·calclJ.]]gdo[i)s. canbe catrled out. ThCfC,~ sults will then provide ILlS w.ith thekind of ql.l1l!mirndve u'-!id.e.rsrn'-!id~.n,g of h)~d:oogen. i.o.[I.behavDo-r

1[38]

tfuat: is essential ill biologyand medicine.

2 .. ]: DEfIINI.lJi~:NS: IONSf N:ONEIUECT!JlOL'r'TESf Sl1RO:N6 A.NID W!EAlK IEIl.EC;l1RO:LVfIES

Mlliny subseanees, when dissolved. in \Vl1Ite:r. dissociate ]nto d~l1I~"t pl1ll:~ides called ions, For ~heM: 5ub5~!I!nCe5~,~he,"e£Of1l!, theprocr;:ss ofgo~ng Into sollltUonln wate[ IS more than a simple physical prm::e:ss; iris '.l chemical p.wces.~ inwhich dle:: I[hemicio'l.~ kklJJidty of the 1110le::cubif spedeschanges, Suhst;a:[llL:ts that d:ussodaJte to for fill ~.o.I:'IIs are called electrolytes, il:[ldl ~:t is 'GOIn:-V'e[l:ue:n'~ to sllbdivide them .i:l'lto~wo classes, stro.ngand weak, Suhsta:l'll.~es~hat do not: dissociaee in this way aee 'C.'~Jledn01.1dec~l:o~y~es, and they a[e of vc;ry lu~de Intr;:[est: I.n ;I.c.nd':bll'$e dlelni,~try, ex;<;e]:lt iasofar gs[h'!:T affect water concentratlon (osmobif~q~) or alter the vdJC orr pg[>lme:.te[s such as disscclarionconstants.

BeC;lJust;; a 111aj10!~ featuee of lon;$U8 thd~ch!l!fgr.;. ~t iscucs~O'ln!l!f}' to eXI'lir~$S their concr;:nt1,,dort~nite:tn(lS of moles of Ch'.ltbll: :ifg,ther th"itn. moles of io'It:O.ms. One: equivalent of an inlJJi .bithait Jm.otl:nt thJt w[lt;a.i:[ls, h'it Is negatir .... ely !l::]]J~":td, or is missing, :ifn~ Is po!Sitively charged,. one mole of eleetrons (6 x W~). for univaleaeiens, eoncenerasion in eqruivabus per Liter is the 5~me $sconcenu~,don in.molesp.e;r LJ~er. ~Fo!rail1 n.vll!l!Gt ion, conO;:G,tradonun eq~uv~leG,tsrer Liter is jll&<itlJJi. times the:: (30!l1cen~l"l'1!du[l .. i:[I .. moles :p.et jf_jite::t .. A goluitinf.1 d.1:;1[[ hgs '.l I[u[lce:,ft[:rndon of y t:qn:i'!mlel:'ll,ts per Liter of a:nyiOl.nis said to be "'y normal" in. th:;t~iol.n,.:;tbb:revhtbedl. yN .. For exan1ple.0.Ot 14 KtS04 is CUJ2 N]fi [(' beeansethereareZ K'" per mole, and 0.0.2 N in 5042.because SO/'-Is biv~leG,t. \'We shall use the oonventuOt1!1!l sy:l11boh; [X.] frl()hl here on ro [~pn:seGt dleco1'lceil1t1"ii;Ion .of X. un equuv~l.eG,ts per Liter, which is also the oom;ent~t~(ln of' .c:h;a"ge caeiiodl br X.~nmo~.e"~ of de:citITJo:[Is {+ ~Jo:[ .) pet :LUtL:if.

Stro.[lgelec~ro])~beS Jfe aJl\'!,I'ayscon!~pl.e~ely dh.sodMedl. in oollli!!loi:'i. SO thaJt the p:arerlt substance disappellillS when dissolved .. in ~~er. Sob.u~ons of serongelectrolyres eoneain onlythe ions d.e'ruv~d feQm~he pa~ent subSii;amX$,. eone of thr;:qJ!:ndi5;.,,<:od<IJted parent moleeules, There-are; fo!!: e:xample::, flu Ng.CI moleculesjn '.l solution of'eommon S5J~iI:. JUSt sodiumines, Na+, andchkuldc

'''''''''~ C:I- (""nd r." ·t·- '.' nd '[-]~' - ."', fO. ;[~].-)

'IW'.'.'''" ~ .•. ~, . \eV e.[ au ... :l ..... GI. ~....

An i~]lpOI:~;mt> and ft'eqruendy overlooked, OOGsr;:.qil;il.e'nce ohhis !l!specc of strong deccmIyre sU~I[]t:bns L .. thaI: .ii!pmh~biH us from] writing some ordi.n'.lit}, g:lJJiQ. ol:he[w.~5c lc;gititl(lio'ltC-~.GDidng: !Che.mnc::Jl reaction schemes.For example, whea we mix a so.l.ntifmofhi~~d:fi')ge.l:'II. chloride, Tiel, in \VlMer,Cl1I]1ed. hydrochlosic acid, with 11I sO]lJ!tion of sodium hydmcs:ide, NaOH,. the t:ernpt;[tion is rowrite til isrea·c:tuon~o i'epr-esen~~hemixing p(1)cess;

fIlC!i fJ 0' fJ IN <lIel

IHO

~

In f'llc~. tbe "NaO H" solution is a solution (;ont'1l.ining Na", 0[:':1", Il:i:ld H'I ions.but :l'IIO NaOH,. ~ifld the "Hel" so~udon oontains 0-. OH-, aifld H+ 1Qns,. but no I:-]Ct Af~er midng, w.e;h;;Ji.v.e; a

[39]

ooitl!{ioll! tfla{~ ww::.t.ins Na", Cl, OH, i1Ind H" ieas, but no Ni1IC.!, The only chemical reaction thas has occureed isthe r-ead~UCSUl'l!r;:nt of d]~ equilibrium for. \.'i';lJl)I;:l: dissod.a~iQn~

-"['~e N1lJ~ and CI- haLVe not taken part in :any reactionsaed [10 N:aC~. 13 formed; (2 . .J.[)is SUfi1P.~)' ineorreer,

It is d~Hic~]]t .1lI.O~ to bemisled b~' the sloppy COrt'ire.u.ItJoln1lJ1 ·~eml~.no]~ .. y that persiseently invokes s~]chnone:-;,;I.s~en~ e[ldd.esun solution as "sod:nntl1 c.h.loK.ide" or "sodiumbicarbonate," but ]f is essentialeobe clear i1I!bo~W1.: their stdcdy imagil1ll!}' s~i1I("tl!s. [dea~}', we should refer ro a soh,l!ldO[l (lfNaOHadded to \.v;lJ1;er as an '~Na~ + OH- + I:-]~ solii;iJt~Q[lj"r;lJd1er than ~5 ;m "N~OH S,{l\ll[]ldO!Ji.'" Kit L~ often useful to GOIIUp~0I11lLosi:: brteferd:'lg: to :JI:O. "'N:ilOI-]" s.ulil]Jdo!Ji, or g '"KCI'" sf.~.lt1do[l. to l!6ep these facts al\,vaysbefo.te -lLS withm~tlos~.ng~he ObV.I01IS 'GDn'l,1'e:[i:nence of the oon:y,emiorud name without quotes.

Ions such as Ng.4 or G- that ate dc;tt".uv·cd f~ol1l1 $~rG\r.Jig dcc[.rnly[cs :iI:l:C Ll.."dl[].].~rc:il.llcd stwng ions, to remind US oftheir special status, T11,e most common suong ~n[ls inbiological solntioas are Na~, K'", Cl, Mg~+, so t, Ca ~, and a ie\v organic acid anions, llotaibJry Ja,c~i1I~:e-. Ucti1lte- io]] fUI1i.c~iol)$' asa cs[rcQngacid al1i.ior.lbecause (Jif d,~lar15e dLssod-ation .cO[l5t!l!t1:~ of laetic a.cud (SecdO!Ji. 2.3b),

We.aik: eJ!ectro~yresare snbseances thatonly P9JJffrl;wlly disscciate when dissolved ~.IlI. W9Jt:e:lf. so ~hll:~ moleeules of rlle parent substance 11IS wei] 11IS the pmdli.lJ.c:~s oi (]]ss{lciar~on allesist toge:~her in 5O:h,l!Il;~O[l. T\lkil:lg ~. weak acid, HA,as our prototype ,!;Mes.l;:elr.;c:no~1tt;,. we canwrure th isrescdO!Ji::

Bquillbriemrequlres tlUt the tate of dusrod1lJtlO[l equal the Ute ofrecombination and leads ro this qJUi1Irt~iJ~a~ive requiremesr onthe oollce.rn:.ra~ions of thethree molecular species:

(2.3.,2)

The.equilibrnnn ccnstant, K A is usually called the dissociation coastanr, Its unit in this case must be eq~Uvailer.lt:s pe:~ Lker.

Tille equJI:DhrDll:m constant is e:;,;po[le:nti1lJlly rebted eo the s;tattdil:fd free e:[le:~-'J! cha:[I~~ per mole forthe reaction. so dli11t i!11uch ofthe analysis presensed in the following dhapterscoui,d a~50beexpr-e,ssedul)~er.l1];S (If [:r-ee er.l~rgle8r.auher Uh!l!l1 eglumblt'.u~m constants, Thorough and usefel qml:!JiitiitlItive g:!Ji>l~yscs (JlflbfJdy~j]uid d'ClnL~[rr havebeen earried out iI].~i:!Jig free co.crgks.

1[40]1

I~u5 importantto understand [ust what EGju<ltiO:nli (23.2) does <Ind. dnes not s<ly.Wh:arrut sap is that no matter wh;;)Jteisel1hJ!)' he Inppening, dIe :r.lil]metlca~. 'V;;)Jl1nes of the concenerstioas of H", A, and HA a~e~~ililbr]u:rn mmt sa~is[T d"l is equati.Ofi. By ]tself. f~ does noe say ·\l,:tta~ 11i:lr of those v;;ill.~s .tnll,llS~ b~; it dJo~ [lot d~rermin~ jlrny Qf~&b~II1, ]t nCI!~IC[;&y ~P[~~?8 Oif)~ of d.l~ n;CJl,l~r.:eII~~n.ts that they must s3tisfy;What dct:c:ifmincs the: actual V:;,l~UcS Of[~10Se COnlice:;[JJ[t<ltinns is the: fact that they must e:adl s<lJtisfy a. number of S!J:ChlfLquitt1:irlC,nlits si nmbllle:ous~y '.lI:ndind!eperadeni!ly.

D~$sociation l1;;u:~ionsplfOc:e~d Vl;li."y r:apkUy,ilnd e:CJu~lib[uumis ~Ji,c:hjeved whh h~:~f~jI1~1~$ on the:: ,o!ifde[ of [illic.ro!'e:cOnlid s or. k,s. \eVe:: are the::ifdblfL: ~U5dfied~n :a1,v."Ily-s. assl[]tlCling e:G1uililbdu[[l status fur such reactions 1:[1. hiologka] aolutions, Carbon dDoxidepres.entssofi'leinteres;~ing complicarions hi. rhis wmez;t~, hu~ t:h.ey are ucSwHy f}tke:l'lcare of by tile enZ)'file carbonic anhydrase.

A qUlIndty s>omC[~111CS u5ro~'O describe the status of:a dissociation cq[I[]JHlbdu[ill is the de:g.lfL.e of di5Sod;;)JtuOin. symbol oc. defined-as tbeconcernradoa of one of the: produstions d iv.klied. by d~e rmal eoneeneraeion of the \\~akdecn:olyte I.J:resem:

[A.] [!rnA]

I[A ] I[Aom]

(2:.33)

Here [1l.,'\)"I"]= [A-] + [[:':lA] is the totru. m[lcen·tut~on of «A" p[e5en'~ :~[I the t'i)j!Q forms, HA ;;)J:nd A. Because by definition there are no other :re:a.ctions in the sohMion. ]W'o.~v.i]'lg A- or HA,. there ~~.t1 be no cb.jlnge in [~Yr] ~xoep1; by ll1!i1.S5 t~.t1sf~~ of ~i~h~1: HA (U A- intOCl~f out of the soledart. [A,-t:1r] , in other words, can ollllybc C~g:nli.bfLd from outside [he solution, so it us an externan), wlilltooJled, orJndependern •. v;;)Jri:ahle.Mme 0[1 this in Section 2 . .J.and Chapter .J"

The d~g11;~ of dlusood~t:ion :ma\y be exp[~s5e.dl~iri;her ~s a pef()~nt~geCll~!il.5 ~. dr.;d:lu!iI..l flfac:~ion> Tlms,if mndidolll~~ ate :suc:hiIhllt Il.A-] ;;; I[HA] ,[l1en r.l.Jt ;; 0.5 OI[ 50%, anlid the weak <ldd .is 50°/., cHssoci:aitedl. Under some Qond~dons •. motel{amp]e:, :a [I. excess of strongbase ·c;;)Jtiom such-as Na.f 00 tile :so]UJil:i.on,. a weak acid may be essentially aH inehe dissociated form. so O:;A~;pproaches to. How does HAno'w differ fil:"OI11 ~. S~fClng ~dd?'[h~ ~nswett' liesul1Ul"S~ron5~ toil dljlng:e in the c'ocnditions. If '"Her' w~t-c added to the solution [ustdescribed.uhen as let] .i:nlic'lfLa~~ed> A "'"'GuM convert to lIA, 0:,\ '\vould. decrease and WOll]d ;;)Jpprora.ch zero as soon as [CI.-]eKceeded [Nra."'] .. Simi]ar changes would notbe observed in [Na·"II;. Na.-I\vnu1.d remain as Na+ regardless of [C]-j or [A-J. Stl5Cll1g dtectmlyre$ remain ool1lpl~rely d.is~Cl·date:d.Wed;;: d~C:~li."Qly~s ~h!il.nge~h~~r degfe~ 0:[ d!issndll[bn d!epending on GD:nd!i[[.of];s,. e::ve:,n[hoUJi,~1 they can beccmpletely dissociated I[]:nlid~r someGOfid:utnofis. Thus d~Jft:rence .b pmfotl:[ld1y ~mpOttafi~ in understanding the a.dd.-b:ase lbehavior of bioJlDgDCl1l] solutions,

This srrong-weak d:~sti:tI.c[:[.on that :us 50 USdLl~. in lIdd.-base chemistry should not he confused with the ordinary-langaege use of the same WOirdS~O refer toconcemrsticrss oftento hydrogen ioaconcentratiens, ttl m::id-base chemistry, strong and wea.k aJh'\1"llIJ1l referto whether a subseanee ~s one {lI1f II;h~ mb~trkind of ~~ectliO~yre, and cannmb~ usedas ~djecdVl;s rOlf 50~U!ti(lln5, nnure lIfld! ·OO11cerat:mtc:drcfe::if to sduti.on~ s, Thus we CDIllId have a d.i]l:IJte or <I. cO:nlice:rttrnited! solu[:ion of a

(41)

s~mng or a \v:e~k 'a(idL IJn['On:lJJnmdly. in ordinary speech, a s~ro.l'lg salt solution means a conceatr;;t~!;d on!;. and rll, weaikadd solution Il~eal:lS one jfl'JJ, r h~:e:h th!; hydmg_l;n ion C'OI1iiC'e'r.ltrcadOfl ];slo,,", fo!!:' wh~rever~~$Ofl,andlr~~iEd~~ss ofwh~the~~he add in q\lest~or.lis 'S~:l:ong O!!:' w~k'

It' sh0wd,also beclearthaeehesnieally; the s\:rongc\Vea!1;: d~ss.i6,c:a;~iotl does 00\: r'e:l'1ec:~ the existeace of r ..... o disii;~:I1il:;t ccat~go:des of SiIlb$tam;e'$inr.lrlljJ;~r-e, bee Lrllih~ra '$pecr;r~m of diesociadO[l, constant Vd!l!C8". rot l[i{]':~ogiGll pl[]:rposc8, any substance who&!: dissoda[j,ofl ult!is[iilm is latget[han about 10-"1, E{j/Utet wiH fmlCil:i)[l[l as iii. 5i1:wngelocil:fo~rt:e i:n,bid.ogk:al so:b:~~J:r1s> g:[ld a:nythi,rII.g with a, dissociatinnconstant sm1l!]let th1l!:n about '100-12 ElvLite:lf is effec~iV'd}~a,rrlorrldectrolyte. Anythjng in be,t\,~en~hese limits is a wea,1I;: e:.iJectil:dyte"

In jll1iY 11.laCifQ&COpUC$rlllnp~e: OIfany aqueo'U'~ sol.!.,l~.uon,. th~ SUIn of all th~ posi~.Uvdy chrll:r.ged. inn, eO[lCCfI[:mJtiU[l1'l 3]way5, c<JIUiilJs thc: sum of all the []cgati",'c.ly dIatged lonconccrussrions .. An a'fll6O!l);s sohuion i;sal~)"S de!Lt:ifUcaJly neutral.

'~M'aC(1)500pj,c'" in thus strllltel'l1el1iltl'l1eans"~a[~ ~t'lo~gh that ·CQ1'l,c:r.mtl:atn01'1 can be In~an:ing .. fllUy de:t.tl:n.cdl." Con.a::pt:l[]iiI~" il:hCO::1tetk3~, iilrtd. pr;llctiml ptobb:w; :adse~[I[his eO[ltCJo1i1: i[]side a:J~5 where Ve;h";,'st.ll.al]cOfi1p1l!f~fi'lenltS areofoen described, such as .t.llitocho.rrld.[ht, presynaptls vesicles, eec,

This :tl::C]ui,r,elncm, that Slo~utiGn.~ be docui.ClBy l1I.cm:I:'3~, isnos only important con.ccptml~~' .i:[I understanding \'!lhy theybeha.vt::1:> they do, k is also usefulinthe qtla:rrlJtid",-ealt1:a]ysis,. because h provides ~ ]]nk be~ween d'ieconcemrmions of the nonresceiag S(l'Qi:l:_g iO]]JS aI:l.cl the equilibrating '>N~rllk ot'1es, I;~s ph}"skcal basisis Co~b'l'llfu,'s Jaw, which sped!i~ the ve:rfIM~ d~ctdC'aJI fo:rc~·s that come i:nito p~."ilY'\i'1I11cnCVLI[chatge inll]b3.b:[lCL occers, .An ·exa:ment discussion of tlh~5 il:Upk rot the reader who wishes a more detailed treatment .may be found in GflJgge:nhdt.ll 1[3~,

Amos~iinpon:al1iil;w[lse:q~~nCt; of this p:rjnd~1~~i5 that itis not PQ5Sib]~w' rllddl a singl~ s:pc:des of ifJ:[I.~D iii. SfJ~l[]t:i~J:r1 :aUbr itself Some other species of uppodt:e chiil:rgc: must :a~,'I.l'9'~"8 be ad.d!ed. 1l!ot the same time.and irs amouet and id!entitr must be incorporsted into calculations

of [:he fina~ result of such addisions, M.dil:l:g Na" as "'Na:OH"has ~, very .Jifier:em effec~ on a sol~ldor.l fiE0111 rllddung the same rllill0~m~ of Na+ as '''NaCI::' f'Or examp]~. I~us sut']ld,~il1i~y ~s,y to OVLI[~o{lk thisreqeisemenrwhen attention is focused 0[1. :a single: inn, specks, paraicularly whc,rt eJ.:1l!:mini,f]gl:lit:irn'iilb[ane~:If1l!:rrlspo[~ processes.

The '$tr-el1ig~h of the eJ.ectrkca~ I:l.eutnlity r-eq~ir~1eI:lt: il1!lly b~ dr1l11ladz~d by the foUowil:lg Glkubtion .. ]nl<Lgi[lc a smallsphere of lldultion, 1 1110.1 inradius, eO[lJta.i:[ling to ',,: 1('-:1 EC]/Lhet escess positivelons over negative ions. The vol!l)me ofthe sphereis 4.2 x 10-~ liters, so that i~ oolllt:a.ills a net positive ch~rgt of <lL2 x 1 O-~ x 10-7= 4.2 X W-13 Eq, One equ.:i~lale.l'l.t: = 96,5000 C, so~he charge on the spheee ~$ 4,2K 10-1.> x 96,5000 ;;;; ·4,0 x '~i)-~ C Co~~0'l'l11y's law in ~].eCii;rcOsta'~ks S3ys[hiilt thcpotc,ntiiil~ on 3. sp:hctt: of'tadil[]s[ (InCltets} cU:l:}'ing iii. d1."iltgc Q (clJlllLlombs}~s Q/Ct'~ 1\: W-w x t) (vo]ts). Sulbstumting the above values 00.[ If and Q. we get 4000,0000 V, almost: hal f 1l! mi]]j.on! The chemically insi:gn:ificam' cencensration .: difference of 10-7 Bq/Lirerpreduees an

1[42]

enormous electtical eifect:.iBecall.lSe ions in solueion are free 1'0 move alhmNt:,~hey will of course redistrlbllJ!e themselves vuyrapkUy in n:':spot1se to 'such eI~c~lt'kal fOf~S. 50 th~t electricalneutf:al kyis maietaieed to ~nt;xtr~m"ly hig&ileVi;1 Qfpr~isklll at all times,

2.5 GIl!:NII!RAL IPRINI;IPU!= CO:NSII!RVAliJlo:r!l Of MASS

C01l~~dOfi 2;; That: substance ]8 generated or destroyed by ehemieal .reactio]]Jswid'1in~he soludon,

T1l.1;S is such J basic, sjmple,aofi'll11o.[lse:rrI.se, obvious idea th'HD~n.1ftr seempedantic to mentien ](. It turns OUit to be extrelllidy ilupor~m]~ to understandthar in discussing fu)drogen ions, CQl1d:udot1 2,. notcondidot1 1,. ~,$ ·~ht;;Uill1':lQrtalJi,t O[l)t;;, MllC&i of the C'Ol)f~sron and CQnc~pt:ual difficukics hI classical :acH~h3se t:heo/IT arise fwm. the [[lbt\11k:c::n idea thai: or!!.ly cU[ldidu[I ~~. :il1Jpli.~5 ro hydmge:rrI.iorrls,

When Qn~yCQndudQn 1 ~ljJ)lies,.as is :allnos~sj.\li'ays~he case ro[ ~nQlJigion&, OIJiI.yvt;;ry sumple addith .. "C bDokkeeping oil the scpam[encJ:olccui.tr 1>1Jcdes isneeded 1:0 explain :a:[Id. understand eencenrrselonehacges, If we add! x IE~ of N:;t+~o I Lirer of so~U:tnOl.n •. then [Na~1 increases lby x Eq/Liter,

On~h~ ot:he;1: hand, w&ie,f1 chemical reactions such ;,15 d:ussodllt:iO:[I. andrcoO:iJr.ubi:[Il1i!it:mclln OC,.. cur, 50 tha~ ccndition 2app]De:l<;~hef.'ll we ba.ve much mo.rewmp~kat.edboo:kkeep.ung to do, Par example. ifwe ad.d x Eq of HA (,0 l Liter of so]m:ion, the wm::en~ra~iOll. of HA will nm: go up by x Eq/LJter, SOl"I1~ of the add~d I' .. ]A w~.ndissQd;IJre to A ~tld H+, but the ~xrem; 00 which this will happ,e,n d~:pc[lds on several oth~t CJjllll:[ItU[ies i:tii. the suliUJtiu[I,l:lot [ust otic. ,\Xle C!1:[Itmt C'I..'C;[1 e:Kpect th.at [H"~ willincrease lby~he amourn of this d~ssO!l::iado/.n.eve[) thcmgh tha~ produces hydrogen ions. How (.i!) cakubte [use how much I[Fr+] will clm:l'llge. 00 such-circumstances is wfua~: tfujs.boot los all ail)lJUII.:,. A~~his stage,~he jmportant: point iosdmJl: we canner take for graneed rhat re~cI~lJig subsesnces suchas HA 0[: [-]+ ·"""ill b~hrlll'lle ail!dutivt;ly in sohnt~.OIJiS even though IJiO[l:r~Ct· i:[Ig sub,~t:3rlJ::cs Slmch as Na+ {)It K~ dlo.

Anodl~~ ~rplic~tk.m (If CQl)sefY~t~QIJi of .h1a&s~h~t w~&i~Vt; "Iif.?~dy ucsed is dle dle!ln:idQfl of [i~'J1LYD'] in Sccd.u[I J:.:!i.,.h Even tlmugh both HA and .A: ate .tellcting species, the faet thattheir sum is independent of those reacrines means thai! [1\(",] only has UJ sa~usfy cU[ld.iJti.o:[I. '~ above, Foea weak bsse, BOH, that dissociates to B~ 1l!:nd OH-. \'l}emaJY simili]a:r]r define the MtliJ] qt]a:rrIti.ty of "B," [BTIrr~' ~ [B"] + [Ofl~.

[43)

espeee their m]liga~iye properties (:0 beappropriate integer rn!.d~iples ofehose of noneleetrclyres a~thr; 'S!lille molae OO£lu;:'enltr:adOl]cs. 1n (ac~. tlley are l,lsuaUr less thanunreg~~ i:!Jl'Uldp.I~5:,

and I;h is ~cs SQlnr:I!~tii1l~5 ~n1Jl]~o!.,J.5~r~nreTn;~ toil)dica~ f!:al;;t~Ql]al d:~5sQd~jdon. For ~xa:nr:J!p~e, becensethe 11101.at freezing poi.lJlt depocssiu[lcocftU.ck,nli: fnr water is 1.86!;>!11101c!UJtu, NaG or KO diseoleed if] \V:a~et shouU give S.o]I])tiDIiliSV,:rJth freezing point depsessioas .of 2 N. 'L86 = 3.72 °/mc&e!Li~er, The observed freesing point ofO.u .M "NaC1" solution is -0.316 °C Tille ratio of l1~sur~d to ~p~G~r;d f~~zing point d~p:r~S5ton,O.S5~n~his(;!l;ie,~S il;;an~d th~ o<stnotl(; oo~f~ ~:k:Cctiit, \'i(lh1l!t.k means js that the N;,l+ and Ctio115 do :n:ot cJmnge t:he thermodynamic m::dvkr of the W::Heta." much as the Sll:me cencentration of uncharged mok:ctl]es does, It does not mean. ~hft,~ NaD rnolecules ~re presenr.nor does ]tte~~ us wh~t: d~e effective conc,enmlJtions ofN ~+ and 0" ar~ in the solution,

Measured dep1i[tn:l'es from '~ndeaJ'" behaviorsuch as this hll.ve ledeo the: ot:oncept of thermodynam:ic a'Ctiv](}" or e:ffectiveconcentra~ioll. and. snicdy spe~ki]'lg whene"'o'er we discuss eqaiHbda '~'e' sholl.l!H use acdvides t>l!thr;t' than conc·r;l1tt>l!tions. Equilibrium states by d,el~l1~tion ~;~ deteemined b\T activides of reaetants t~the;r t~!I;[1 bv eoncentrarioas. ~]rIS Cl];,~tf"1l1111!:tY~O nli;[I~mize

r!' r!' r'

the d.~stit1ctio.li]. bet\veelili. t~etii.'iI, eSlJ<6cb&ly in. if.'iltrodlucoo.[j! UeatlrnI.ents SI]ChaS thUs book attempts

tOO be. andwe shall keepro t:hat convention, FOrmtml'e.ly, strotl:g ions, which are the orli.es in h~ghest W[lI!;~nt.'nldQl]sun bk)~ogjcdflluids, do not gr;t1e!l'ally p~!'ddpau~ to amy sl.gni~k'al)t extent in. 1I!;[IY chenoical c::quililbrh, Nflnethdess~rrhe dU5d[lni.Otii. between mcasuredconcentrsrken and lliLtl.'l.dJty o[ effectiveeoneentraticnis iJJ1\vayskuking in thebackgrorund. It shou]d be ca[dl]]1y esamineel whenever dispa.r~~ies arise.between simple theorr and the results of measuremenss, For most of the analyses in this book.we shall asswneth~~: t~e distinction is not .i:rnpor~'l1m and. usethe '~yn~bO:~s []~O mean d~het' OOI:JI(:!r;ntradon 01: act~vi~y, whkhever is !J!pprlQpri;lJte, a~\lla}'Sull e<JIUiVillk:nts per Liter unless orherwise indiesred,

Otlr;p~ace in. whkh the distinetion be~ween !J!(;dviltY!lfJd OOfJ:CII;!I],t!l';Idon is cuStflinrl!J!f.Hy tn!J!de exp~udt is i[l. t:he: spedfiimtifJ([1 of dissociation cotiiS[1I!fits. \"hen. the: cfJ([Istantls wdttetii. with ;,l prime, 1I!S K~A,[h1l!tQ(J;[l'!lCtiitifJ;[I11!.~ly~n:d:k!l,tc.~[h1l!t the: value h1l!8 been dbtained.I[];n:de;r experimental ot:tmd.inio..lilis in W'hkhwnaentrntlom., have been measured. ~]t3 value can. then be expected to change wit:h wncentr:a~:ion.s of ne~.c~~nts., becauseactivieies aregenerally nonlinear funcuons of.conc·r;ntt>l!tions.When th~ dussod!l!,tion QonSii;jlnt is 's~:Jo.edl~,ed withour the ~jf.inll!t;,. as K,t> the itnp~ucatuort h that g.dnvi~j,e,s .ra~her thenecncenrraticns s~loiliH'be, used, and~hen itsvalue can be expected to he OO.f.'iIStll:lilit: over 1irn:lilige of eoncencrsdons. FO:RlLt1Jtely; these di~st~m:tjQn;s are seldom .impo.rtant in body fluidsbecaase of tlhelJdll:~i\'eIJr small changes in wncent:r:a~iorli.s of 'J<'l;!I!k electrolytes th;I~ they gel]er:al~yr;Rpede'ncr.;>

.2,.7 SUIMIMARY

'L The: gOg~ of this appto1l!ch~o acid-base chemistry is toestablish the: 'qu:lI:tiidta[uve relatioash~ps that detf::I']'l!'iun.e [H~]i:li]any solution.

2. SoliUJt~ons are del~l:J,ed 00 b~add if [f.]t] :> [OH"], alk!1l.J~I]~ ~.f [H+] « [OH"]j.!1I.l:Jd neutraljf

1[44JI

I[I-tll ~. fOHJ.

3.,. A substance js ealled <ltl. add if it raises the [l-[+j';!.?ill.c.n. <lddbd. to <L 5o~ilIJtinn. <Ind. a base if lE loWleJfS [H"].

4. SnQ[lg elr.;c:~m~1tr;sare wmple:~r;ly dts5Qc;iMr;d ~I] 501il;iIIckm.We!lil: elec~:tt'O~r~r;5 ~.Ite piUd.y dissociated and oibcr a dissociation oql[]:ililbdu[[l. No;["]de:cit'[olytc.s dlo[l(Jt dissociate .into ions i[l. solutr.on.

6. Solutions .t.T.m:lt lbed.e<:tri.caUyn.eut!fli]'

7. Conscl:"vatbn of [[l;11$S· <lpplksin Il,vo di.ffc.ttc[lt "vcays.

8. Di's(:I]].ctkms between activitiesand conceutraeions of ions ma}"be ]n"l:porra:nt in some situations, buuwinbe~argely ~g[loredu[l.~hi8 e]etnen~~l)r~:tre.ltlm;'[I{.

:~. DallJtxig CD, Dd'ia,,-ern. JC" CODpe:t I"j ohnsml. Sl\f, De:La:r.um Ee"KrullJtet lIE, SruttL~ CF~ A ttm~hej.n8tuC81 ]nodJd of the- hlJJi.nmli tE:~pLrnltDt.Y ~yS!teli.n, Pels-peet BLOl Mr=d ~324-37{i"l %~,

2, .M.alo[ley pl" Dd'ia,,-ernJC, Def.and lEe, Bhl.dh.am CD: E~:a~I.e d ru U8~l11l0(M ~h1:1I1.iLl.a[[m1i oJ theblcod b:bd.tet'nicai system.§ Ch~Oil:ic Dis '1~M41.4.25, ~%6.

3, Guggenheim. E,j.; Ti.'l!en["ody.['I~.mk,s, :lin Ad"'"'"I1need Tre~l:meill: ('Oil' CI'l!emj,sts ~['Id. Ulhysidsts. }tms!l.eid,a·m, NOfth· HolhnJ,1957, Pr 372-373.

[CHAp:TER ,3]

The Simplle'st A,cid-,IB,C1s,e System:::

-

P'UlreWater

Peter .A. Siewart it

'·Add·:base'" 11lealJ;S"whatllllppeI]S to hydl5og,en iOI);s .in.s:g'l)I.eQqJ!S solutions," 80 thatthe

first acid- base system 'We must undersrand, and the simpleSt, is water .k,osdE PI[]:teHGJuid '\,\,~t~t

is a sl.lbst;Wfide w~Jth ll:[i:Ofi1:;Llm~s. phys~c:;wl propettiesan.da. rol:l'ip£e:i::st':Wds:~ic;wl stmc:tm~e still not oomple~ely understood, Many of il}specu]i01JJ(' prope.n1ies are eraeial for life, and. it isby :far~he 111 .. jor COl1lponr,;nt of alllwing sy.stel118 [1·3], Ias ~h!Eer; most .inrere,$~.illg Ij!EQ~':Ie[de,s r'OiE add-bast:: (h~t.n:~st:ty grcnit5.btg~ dkkctdcOO115l:ant, irs vcr~' 5m.'AU d.issod1litill!l:.CO:[I5m.nt,. and~ts '\i'L:if~r high ro[i:cent:r:a.t~.O:[i: ..

Tht;;~arge d~dt9ctr:ic: OOI]S~~.t1t means th .. ~ '$~bst\1i.nc~swhose molecules ,c,01n\1iln 'stri}l]gly ionic oonds win dissociateto someexrenr wllic:.f1 they diss.ol.vc; .i:[I. waterto yidd soludD!11scon[g~:[Iing ions . .subsu:nc:es. that produce hydl.mgen. 0.[ hydro:8yl.iD.n3 in this "V'a1J,' wHI be p;Wtdctdll:f~y interesting for O!I.M purposes.

W1Itc.r itself dissociates illtO&!Jyd.l:og~n g:!l:d. hydtoxy~nog~. At 37 9C, {Ili~ d~5sod.1Idml GO;[]Srn:!l:it is 4+.3 X. 'HtL~ Eq/Lirers, so that \V:at·erls al.n.O:lUidecuolyt:eby the dl.e[i.n.~do:lUi. oftbe p~eceding chapter, It isa special case, however,. and. ehebiological impo.rhl.nce of this miniscule dissoeiaeion OJil1istan~us out of ~:II P"O'PQ~r.~.ii.on toirs '$t.nall.t.na.gn:u~udJt;,

The concentradon of"l1ll!teJf is about 5'::'.3 :rut ':Wt 37 "'C This is. almost 400 timesthe concentration of the next most concentrated substances inbody fluids, sodium ions at: 0.14 M extrazellu~;a[~y and l'l'O~S5iUfn lOI]~S a~ 0015 .M ~if]ltt'S,c~llu~ady. Hydrogen ~ons in bo&y ~Uld5 ~.~. ~. lIliOU$~.tld mill iontimes .1c:5~~ oDlJc;e,rnltii:akd than "Vl1Itc:t. TIlic:5,e, compadso!11s canbe VC:;if}, useful i.rn. simpHfy. Jog our aDlllyt:i.c:;wlt;wsks bter O.IUi ..

In Sr,;ctlQI] 2,2 we pointed oUt~hiiL~ tht;; hyd.iI:-ogr;n iOI] CQm;e.nt:l:atiQI]. .Qf' p~roe "'l;lJ.e1: cllia:ngr;;5 "vjith~~~J(1p~ii1IltI[]ifc:> and rei!: Pllu:c"."mtc;r L~ 'A1'\iWyS scid-baseneutrel, Out gOi1l~ fnr this chapter is to arrive at a. clearquantitative underatanding of \why dlillit isso, in terms of the definitions and basic principlesp'resetrl'ed in the previcus chapter,

1[46]

INI+2

INI+l

I -a.

N·}

Fiiglull"e 3.1. The gEMlieral1 iformof the p,H~I[H··~ rellatio>flSh i P' .. ,· BqUJation 3.1. N iis arliY iiltlitegelt', Dut ill, practfice N is Ifestlt"ik:-Iteidl totthe Ifaltlige (1"01'111·1 to +1l4. La IE~NI ·dle:not·es 1 x 10-w. :5ee figure 3 .. .2 <311;00·.

3.2 THIE. MEANING OF [IH+] .AlNb ~OIH-]1

Str~c~~}' s:peakin:g,. ]t is a]rfl.os~ meaningless LlOta]k of a E:'i}'drogei:l.iDn. meaning a free proton, !liS h!llvi[lggn indr;r~nd~l]il; ~xist?[I~.~ ~n~~q~id w~tr;~.t'iEQWl]s~~tr;!lis~~~r ~ndr~p~d~}'wh:h W"WI: molecules, and also surround the:ru.1:5dvI:8w.ith layers of electrically arrractedwaeer molecules, 50 that o[l]ra. careful ·q!llanUm1 statistical analysiswould provide iJJ precise description .of jast What we mean when we say "hydrogen ion." Noneeheless, a~: the macroscopic chemicsl level d~a~: is ~P'1"'wi:liriate folt' gugntit!lltUvt;lI,l!nd~lt'St!lil1dillg of acnd~hasr;b~h!l!"l~.o~, we need !Ii way to~r;p[~~nt the: avctagc effects of wh31tcYcr .. ]] thei:[J:divBlI.alprmons maybe doi[Jg. l~he sy.mbol H+ and "he words "'hydroge:[lion" should. be underseood in iust: t~b sense, asa .. kind. of n'Le~JP:l:tot for what must be a yery ~omp1ex s~matio:n at the m.o.~ecu]ar level, Similar eommenes ~:p~:)lry to <"OI-:["" and '·h)rd·I:-ON:r~ ion," SOll~eWlt'utelt'S use th~ symbo~ H.~ 0+ and cs,peak of the hydi'Q[I'Ul'l1 ion, as .if thus WC[e amore aeeuratercpeescnratjon. \1{l1111t shol[].ld.ibe writknns {H:(H20}J+if we: W\"Irt[ Ol[][ symbol tn remiod us. of th:epro~od3atttaJction for water molecules .. Both these larger syn~bols are t:Y1Jogr:a:phi.~a]]y mcenvenienecompasedeo H+, so we shall continue to use H~. It should be ljecog~:i:2.edas a srmbo1 for a nleta~:)E:~o:r,. which ]gnores eoasiderable molecular oo.lup]exi:~}T, hue is useful to ft;[:lir-e,s~ntth>er~~r;vgnt chemical behavio!1t' Qfone product: of 'w~t,,~ diisSQ;!;illltu011. M~'an!y

[47)

8

0,01:+0

,*,.01:-7

IFiiIIilIiliE! :3:,.:2. ph'! 'I;o\e:rsUS [114"']] over the p'llys~ol!oglr:Gi311 r.alillge nom 6.S!C0 8.1rllis CjlJilrve may be used as a gn!!phIlcaI callcilJllato,rto, convertflf1om Oif1ie scalleto, tlMie: other In elilllile:r ·dllil!e:cttJloif1i ..

of the: .[jel:tiltf~:aH.l! enl0HoJia.l.at;!1}i.ujje;n~s. ~.i:'b. the Jc:ud.":baS(: ]i~e:lrnittlre seem. tos~e:fi'i. from fuUii];fe to recogeizerhis me!~ap(ho.rica~ status ofH" and Oft-,

Fora vai!::ie~y of historical reasons. i:~ ]S eonventional to express hyclrop. lon.co!1cemmtion. in ~;WD vt::ty d~fr"re[Jjll; ways, ei~he!E duru::c~~' as [[-]-+]1 Of i(]dJn;ct~.y as pH, Th~f-,e~adon$h I~j between them can be: written .i:[I. dlittcc diffi:;oc[lt.1D{:iki:r1l:g hut mathematically cLJjuiV'i1lk[lt forms;

A generalleed d isp~.ay of rbese reladcnships is shown in Figure 3.J.;whj~.e Bgm:e J,.2covers. the spec.ifi.( r~n,ge of phy'"sj:ologic111 interest, from pH 65 eo pH 8. 111]8 figul1e m~be useful for

[[48][

TheoclaJtio:n1Iship betWOCIJi. [H+] and pH has several jmlpoltttllnt cbaracrcristjcs th:ili! GlIJi. ClIil1'iJC !t]:IIl:ne!l:':essary confusion if :not understood dea:rlr, The first is that the :mnl!le:tJ.ca~. va]l]eolf~he .~og1li'i~:hlU goes from minas infini~}" thi'0!ilgh zero to pJIIlS ]nfif:l~~}T as ]ts argumenr goes from zl;~o~hIT)1,,1g&!JQl1~~Q p[1,,15 ~I]~il]ky; As [H+]i[l~~~~;i. fr(l:lll 0 00 ·~,O Eq/LJ~I:, t:h~~fQ~,. dl~

pH decreases from plil!s i:IJi.I].nity to 0.,. AlJiy vdul:m: of 50luli:nonEhatoonElInns ilJiI] H+ has pH ;:::; +nnflnu[y! pHoomunue5 iI:O decrease from Omo"wtt"d l11i:lJi.ll.;'litlf.ltIUEy as [H"]I increases :albove 1.0 Eq/Litet, ~]~ l3\let)! difrnc~]]t to get [[::11 in aqlleo'Us SO]!t]ltiO[IJS, below aJlxmil: 10d~ orabove about 15 Eq/Liter, so th;M the practicalIimiss on the pH. seale are -1.2 and 15. The common textbook sta~r;l11enll; that the pH '$C!I!.1~ go,,"5f~):m Oro 14 h!li;i no bac$is in chr,;tnk:.'a~ rl;!Ii:lu~y, bu~ inr.;~~y reflcets the athiE:rntr appearntlo:: oflno",~[ pH meter sceles, O~dunll:tt"r conccnrtatcd hyrlittfJoChlnrk alcid h~s a pH of aJbout -1.1 ,.

Be~;lJuse pHis a~oga:rjtht.nk ~fle~tjo(] of [[f.]-+]. it Sl101,,1~d p~~miur.;a5y g~phk~l vis;u~H2'~t~o(] of "il"l,dde: rnnge of [H~] values, UnfHii:til!~nlltdr, it d!ocsUt b:a.Ck.w;,l~ds; pH goes. down. :as [JJ+] goes !t][::I, A direot .~.oga[ithm.k scale wOil.dd.beulImd:l less oo.n:fu~jng in th is respect, excep~~h1lit ks VlIIueswould be m.osdy negative, andeherefore would pre!mmllh~y seemless "real"

ArdllltOO p:tiobkmw.ut:hpH .i8 that the dfccdv:ewilJ.o:lJitii:atiolJ. ofH" is 4 to 7 orders of M"ilg. nitndeless than that of mosr other ions with whiCh we are conceraed in bio]og!cal sohnions.H" is, .in t:b]S sense, very ltlucil a "erace substanee' .in hod}'f:Iuids. It is new ii:ln~~t]ve~}' obvious how we sllo1,,1kll~hink ifu,QI,I~~~5 ~h~lllkal. ~haviQ1:" in. 'qil)L;ll itat~ye W~ll~s,By d~;sg~is~l1g this ,!~IT Sl11gU iIJlU'iLG;n1I it:ude of (H"]I,. the pHnDtaEion obscil!tc.'lmllny qil!:amrnltivc m,pe:c[s fyf thech.cmka~.tt"dllJtio:[Ji.· ships that are invo.lved. in aJcnd . -base behas .... ior a:[lJd distorts the aJppaJre[IJt~!u.af.'lldtatwe signnf.iICa:m::e 0[[11+]1·

The eqil!i~ulbri11111 ~tllltes of cheilJllical. l"LlIcti.OlJisun which H~ isjnvolved are detC:;i:.munedbr the ef±ecti\le concentrscions of the reacti.f.'II.g substances, sothat 1[1-1'] is whaJt weUl!:ms:t think a!bout and deal with if'we wish w al:ta~y.~e qua:l'l.tim~iveJryandW1de:m~a:l'ld S},Sten1S of such reactions, F:tlJ!.l11 Ihi$ vie\o.vpoilJllt, pHis :a vety sHang.egndQQn~using dJo1,,1bDy nOlJllunr.;;J!:1t' trcansfort.n;IJdf.)r.I of [Hl Statd:lJig with the Vl'I:rhMe that is gignJinfi.Gl:nJi;t inJi aeid-base :re.act:io1"1S, [1-:[+], YOIl mustfirst

tii.ke i~s redprocaJ,. whuchus aJf.'IIO[IJ]inea.t p:oo.cess, af.'II.d~hef.'lltake~he ]Ob1i;rkhM of the restdt, j second nonlinear process, As a result, it: is yet}' d.ifb.cuhto thillk abo~(: what must be happening gU~:lJlidtauivd.y W (B-I]I when pH values !Ii.Le d~ed.

One prn,gmadc .i~]s.tifiJcJtiOin for usi.ngpH mi~t be thalt we ha.\le "pfl meters" thar rnessure pH <'direcdy." The physi.ca] fact is~h.ll~ pflmerer measures an electrical poeential differel'lice ii;&!J;lJt ~,s, under ccaroe6,l!Uy oontmU,edd.rc~t.nstances, a~ogg:rjtht.nk fUIJI~dolJl of [f.]+]. [1JIil;erpm1ng t&!Jh pOiI:ClJiti:al difle:ttnc;cunE·eI:1115 -of pH ratlacr then [J-[~]I.b ~imp~r a matter of puttilJig a mnelltt",. rather thJ:neJol]J()f.'II.endJ]. scale O[IJ t~e voltmeter.

Th~ surppooed '\H1i~5"; of pHlnaj :at~o C;lJus,,"oonfws:uQl1,Tu showB be dr.;a~ that pH us !Ii dimeiIJ~osiOnJiksS number: pH values arc 5i.t.np~r dhnelJisi.ook55 numbers :a:nJid. should be treated. 118 snch, Al::et1.ectl.c1[IJ.of tbe widespread confusion dut: exists about the ph~"SJcaJl :meaJ:n:nn,g of pH is

[49]

the frequency '\l.7idl which pH is ]noorrec~ly referred w in coneeerrerien units, oreven a.s"pH. C{mcel1u~ado[Jt'! 1[1. fac~. the q[uanthy whmelog:adthtl1 g~ve$ us ~:il':-] iss. vO~UJlne pe:r' equivslens, just thei.uv·etl'le Qf.cfltic·entr'adO[l. pH ooUJld be oon~c:dy seen $SS. loga~uth:lnk 11'leIilS!UI5e of the:

WJIUrulC[(:q[lli:ttd to 'GO;[][:lI~n '1 Be] of[~I+, In b~DOd. pl!ls:m:ll 11:[ pH 7.4,. th!lltvolurule is 25 l11i~.~.iil[l Hte[~!

F~:IJi.aUy, pH suffers from a 5c:1:.1-o1:I. s d!ro.wiOO.':k beeaase of the nonlineariry of [he .~Dg:ll[.ithmiG function. The Ib1ptU[hll1 of the sum of severalnumbcas .b[l:ot cqlJ]:lIliCo the sun] of thd.it~og:llz rithms, Theimportanr electrical neu~ml:utyreql]:ure:n'H,:m for .ionk solutions is necessarily expressed ineerras of the slgebreic sum of all ion ecneeaeraeions, sD~h:!u:pH ~annm~ be used ]n ]t'. [H+] must be, Theequstiou that csew~hlI~ sumequal OOzr;m ~sa.lW'ays essend~1 i[l. dle qUJ.jll]iI;k,,rive analvsis of anv 50]lJ]du[I's; !lddz'bca5e bdl:llvio:t,

,I" ...

Al~hou~~he hisw.rical.l!ea:sotls for the il:mrodr'uctio.l'l. ofpHlIlaybe undler:smndalb]e, irs cont~nUl.ed use ~,s dimcuk to jlUJ5tLfy; It adds much more to ·confmc$ionibou~ how [H+] behIilVe$~h~n to undc:;rsunding" [n this book \VC: 5.hmll use ]iJI(::lI:r [H"'] scales, direet logatlthnli.c seales, and! pH in pIDtid:n:lg gr:aphs~.o s.hrFwadd-·lb1l!sebeh.av.iD.r. The reader may decide WhDdh are the most informative,

3.4WAUIR IDISSOCIA:rION ~QI.lQ!..:IBIIR!UIM :r" ~ W:A'I~R,ION P\R:OD'Uc;"'!i, K~w

As ~:I~.dy~[J!d.k;lJtedI>""~ter' d.issod;lJt~Qn C~.11 be de$c!'~bed by this chem:ic~:~ :r~Ci[:iQ11 scheme:

'Th]S is a very f'1lst' reaction ineither direction, and complere equilibrium m-ay al\vaysbe ass,1.mledunb~ologk~l c$iw;lJdo[ls. The qu~n~u~lI!tiw mgl,lir.-emem on the thr"ecomrQ[len~ .$~bs~;mc~ es at OCJIllililbdunl L~

[[HI] [O~] Kw DlkO][

(3.4.1)

The wa'rer dissociarion constanr, Kw, is higMy~e~uperal:ure depeadenrand ""ery small, l~s v~luei5 L8 x. lO·Lf" Eg/Ute~ at 25 "Cand 4.3 x. lOdf, Eq![Jref !liil; 37 "C

Equstion (3,,4J) Cll:[I. he simplified by reCt')gnizing: t]]1l!!: in rnil.ostblo~.ogi.ca] situa~ion;s.I[Frl1l!,[ld [DH"]I are weHbellow]Or" Eq!lL:ite.r. while [[::l~q ]8 over S5 Bq/Lieer; Wha~: ehis means ]S tihat the d.~s$o,d.llt~ol] ~.l~oces~ :h:as 110 5igtl~{i(;~.t1~ err~c:~ 01] the:"N~,.ef CO[J!cel1~~t~O[l. [H20] c~.t1~hem;~ fo!tC:;bc cnnsideredconsranr and l[omhilJoo wkh Kw inrn a new cOlJsrnnt,K' 'C!" calledtheion product fnC\V'3Ite:f:

1[50,]

lE-il3 -

o 1- ~~~~=-----.----------.------.----------,

20

50

60

F~glulre 3:.3 .. lhie: \!alrl,~t~(m wlillh te:mlpeirattllllr'e 'elf thle walJe:r Ion produlct. II:::' ..... , In pure waiter: Cllt~ from IHlamed andOwe:n [41"

[,IFiI] I[OH] 1[(1I'l1

{3.4.2}

BC:1[3il1.~C: [H~O] L .. :.1lffc::dc:dlb}' dL"5Ql .. ed sO]I.]Jtc. s , andbecause Kw dl'.l1:IJIgc.'l with, te.tnpe.tlI[u:tc;, the value of K\~, \'ifnI .. lsochange vrirh boththese va.r.iailbles,. The value of K> ~' .. lso depends on tfue ionic strengeh of the wlm~iofD. in question and OfD. the presence ofspec.ifi~ ions" The mos~ useful source of numerieal values for. [Cwls the c.l!l!ssk book byf-]al:l:led and Owen [411. In, pUIii;!

. .. '!'5 "'C- 17' - ~ ", 10'.14 (lI'J' 'j'L'I~ .~2: t 3' ~r '! ~ ~0'·14 (lI'J' 'j'L't ·\1

water atz,o ,l7\.. W - [,,~) x , " ,~q" ILe.I:,I;:.1l . - '-, ,b.91 N [, ,,~q, ., e.I:J '

FIgure 3.3 presents enllJ.)]rical db~l1 from Hamed a:l1d. Owen to show thevar]ali'io.ll ()if K' w withtemperature inpure water" 'Jb;e fQUowi:ng fO!tl,ll.U~a!il1;$ dlds cueve 00 'betwr than 1% !l!iI:ldis ilI.~fu]~n ca«,c;u.btirn15. 3,lthough ,k hac. s nntheoretical s:ignHlcano::

where T is fun degrees Kelvin, ]0 selutions, ch:ffemem vahres of K'w a~Jpll:y" The va]~ used in ~!l!lo;;uladons must !l!~ays be that apl:Iir-Qp~i!l!.te toahe :soludon in quesdoG,

[CH!!'iPTER 3,- THIE S~MJllES.T ACID-BAS E S'tSiEMI: PURE WATER.) 1(51)

4UJE-7' 7.,5

c3.m~-"
,-;
~
W
0=0
7:
Q 2,OE-7' 1 :1:'
,~
'II:l
II::
."
+""' [IHI+]
I
=
1JJE-}\,' alild O.OE+O +-----,---"""T""---r-----,:'----r---~ 6.5 6,0

10

lFiiguli'e ~:.,4. The v1:llrfiatiQn of [IW]I, I[OIHo) .,.nd pH w~th temperetuee ~111I lpilne~vater. Right hand seale fur pH, II eft hand sG1:I1Ie ro:r leWD end [OHI-], wlht~c:h .,.re allwm eql!!,Jlal.

Equation {3A2}exPJresses in i1I~JP:miSimll'~e (b~M: good. eo abou~ -1 parr in U hiilliofi!~ iO!~l the d~s$od;IJdo(] equilibrium fo!: "v;lJrer. and rll:-ovid!r;:s us widl 01'1e qq]al1Jdtadverelatuot1sh~p bet,"""el1J [H+] and [OHoj.lnli. order to be .. Me to predict the: values of t:he:>.!:; r,,¥o Gjuan[i[ics."vc.: must h1l!.ve anerher ~plandutiveiDeb:tiamship between them. II: is provided by the ph}sucaJ] :rectuirerner.Jt of electrical ne'U~:rn]]ty; Because H+aitld OF!" arethe 0n~}T ionspresenr; we mus~ have

[H]I [OH] 0

(3 . .5.1)

Now we ha);re twoindependent e'i'uat~o.ms~lfi~he~~l'O unknowns, [H'] and [OFt]l. SD we cam. solve for the.m. I n this, case, thealge!btal iSU1via~ .• but the procedure is the same OJII.e we shall use again. and again in the morecomplicated cases that: m:ise in the foUowingchapte.rs.FmID EC]ua~ion (3 . .:5.,1), we cal1J. s~lhstitlll!te [[-1+] fQ~ I[OH:-] il1J {3,4,2} andw:rUU;:

[H] [&1.~ K "", or I[H] JK"'l1

1[5.2]1

[CH] [OH] K"."or [OHI] JK \~

(35..3)

Eql[]lIltin[lS (],5 .. 2) and (3.5.~ [~U the whole story o:[Eh~ acid-base p:ttupettb. of putt water, Pure w:;tbet must llli"vao/sbe addl- base ri.eu~1rnJ because [H+] lllwatys ~lUll]S [01-]-]. Because K' w is J Stoo.r.ag f'Ll[llCtior.a of tempe:rnmre, howeve:r, the neuual value of [H'] and [0[::1-1 musebe also, F~w:re 3.4 shows how [H'], fOfl], and pH vary withtemperamre in pure waeer overthe same temperature r:a(]~ as in FlgUf1€: 3.3, \Vidl il;hisfigure.';A;,ihkI1 is jll.l!st a graphi'ca~ ~jr1l;:.$~n~~t:iO[l of what E(]uali:nof.1s (3.5.2) and (3.5.3) 5gr. we have gdlbred out gDal of understanding thevalues of [H"']I Jtld.I[OH-~ in p'Ll:re 'i,!,"3,ter,

3.6 UPiIlATIIH, IDEif,INIf,10NS: NEtifRAL, Acn».c AINlb BMlC SoLUrtrlOINS

In Section 2.2 solueions 'i),rere defined as neutrs], acidicorbasic in eerms of the size of [H'] CQlm'P~r~,dI UJo [0[-]-]1, Egluati(.m~$ (3.,.$,2:) ;t[ld (J.'s'.3)prov.id.e ~ .. ~~S$r-el.ative basis for these d~fI(]i~ tionsby ty.~:ng them to the rmrnl11eter K',){"

Definition: a sduti.olll. L~ acid-base neutrnl.ifi.t.~ [Ht]l;;;; ~. Its [OH-]w.m.[helll.1I.~50;:;; JfI(."w.

IDefirnitioma. solution is said to be add, otacidic,. if Jes 1[11:"']1 is gfe:;t~et dlJn JK 'w . From (3.4.2),. its I[Oll] will t1en be .~eS:5 tlJJlIn Jk \~ .

Definition! a sduti.olJl. L~ said. to be alkeline, OI.r h!!sic. if hs [H+] is less tlJJ!!:[I Ji. \~ . Fro:tu (3/4,2), its [Oll] will th~n be gt:t;;~ter. dlan . ../K'w .

I~ [oHm\rs, fmm the (~efin:i~ion of aeid-base nemral thll~'ll1e'U~rnl:i()'" occurs a~: a d:iiffel\em

[f-]+]. Of pH, for.: each sclnticnbecause the value of K'w 1$ '$~:JoeC~~i,c: f'Of each so&uliQl1, For. exlImp.Ii:, in blood pb8!JnJ1I lIEbod!y tempetaii:ut~,. K' WI ;;::; ~t4 X ']O-i~ (Eq./Litcr)l, So thgJt gcH~bg~~~ nClI[rn~meg[lS [H+] ;:;; 2.1:;:10-' Eq/Liit~t,.pH 6.7. "SElIndgrd" lIni:,rb~ lbl!IDd pl.'ISlng has [[-]"'] ;:;; 4 >.: 1O-H Eq/Liter, pH 7.4,. sothat .it Is M. Jlklll:ine f!.'ltld, wl~h [OFt] = 28:.: [H"] ..

TC:XEbndks ofilen eire the~b.b:"l11ub.

plH pOI"! iL"1l

This fm1h1U~!il is o!b~aun"d by taldng log~f'u~hl:n,s ofbmh sides of EgU!il.tDQl1 (3.4,2) ~[ld using the obvious!il.iI1!i1.1ogy 00 pH fo~both pOB ;t[ld l,l(' 'W" Ir sl1Quld theroef'Oroe be wdtre[l!il.s

plH pOIHl 11'1(1''.11

W~c~n~hen seethac th~ value of 14 fo[ tI1er.ught·h;tm;!. sMe o[l.ly app~les when [(; \:i)";;;; 1,0 X 10-1,,1 (Eq/Htcr)~, which is fnr pute water at 25 "C, In blood plg~~lng, pK' w ;:::; 13.4 'olE 37~C. o.[lCI:

1[53J

aW'J:in" i'~ isesseneial (,0 use the value of K'\V ~[jprop,ria~e m the so.lmioIDI,andithe conditions under an!l!,~YSus.

L Th~;ildd':b~®e luopt;fcJe,s ()fplllr~""liltelf ~.Ife'Vt;i1' simple and aee :fuUy desclfubed qll,l!;lr.ltln::advdy by

[1m ]1

(3.5,,2)

[Olm 1

~3,,5.3)

2, Water disso~iatiion equ.i]]brium ~ires that inaqueous sO]Wl:iDIDIS, [J:['] and fOJ1~ m~s~ alway'S '$~tu5fy

[J-I]I I[OIH]1

TIle v:al,~,e of K'w used, must a~,""j,lyslbe t.hllit 8!ppi:Jop:fiate~o the sd,~dO:[lo,i:[lo~~,estnon. K' w changes with ~:elIlperatme. eoeeeneraeion, ionic strength, andthe presenceofspeciiic substances, In, body!1U!:uds at 37I;1C" K\", ~ 4A X ~~I)-I~ CEq!1_jtt:If)~.

3. N ~rml:rail,;iI;ddjc:,ail:ld basic SQ~lI,l!tUon5, !tlfe de~il1ied wirth ft;rr,e[t;iI:l:C.'e to d1~ value of ,,,IK 'w • NC:'Ll:ttl:ll: 1[[:'1+];;;;; .,[K 'w ;;;;; I[OH-~

Acidic: [1-[+] >Jk"w ::;. [0[:']-]

BlIsk: [1-]+] <: Jk'w -c [OH-]

1. Henderson 11. The 'Pitne;s~ of the Envi:l'Onl'1'1~llt. Bot:;ID:tli,lBe:llCQ:t'l 'j}[~t:;s. 195tl,

2. ES~I'ih'!rg D" K9!!JiZ:l'l'l~ml \'Y, The Stfl1~ture 9i~ld P.ro~[ti~;s of \'{f.al'e,r, N@w YOifli::, OdOfd,. 1969.

3. PrliJ~l.e.ks, p, \"I?liJrer; A CCi:l'i'liJrenei:i.~i .. ~e TDefiJ~l~~, New Yo[k, PLeilllu'i'iI Pu;~~, 1971" 19'73 vols 1·3, 4. H~U~l.e{l HS, O~ztlllBB: The t'lhy~~(::al Chi~mj:;:try ofE!ectrolJIIJjJt Solutions, New YoIJri;,. RI:'!i:tllho]{l, 1.958.

[CHAp:TER 4] S'tr'olngl 10'ins

and 'the Stro'ln'g Ion D'i'f'fer'e'nl,ce

The :~ydrl()ge(] ~.o(] oo[J)cenu:at~ol1J of any 5Qh;wtlo[J) Wfi1S outeo depend to a large ex~en~ on

the cO[lce:,fH:rntin[ls of sn:;O!ng ions [h1lt ir enneains, The next lltt:p i[l 011.[ p~ogifd,:sivc 1Inalysis

of biologica!] soh.ttiorJsarJ.dthd.it acid-base behseioris therefore to unde:rsu:nd dlooough.lr rbe properties of solacions containing cd}T s~rong ions, Foreunasely; such sofut1onsare simple to an~:~1z~> &c~Juse s~:l:ol1Jg d.ec~~o~yle5 ~:~ complel-ely dI:i.s5Qda~ed., the on~.y equ:ilibdL,l~ll",,1; have tokocp track of is dl:i1lt~bt W3tCit dis5.Gdateon .. As 11 .tc5uk,ilhc ql[]lI:[It:uiI:3ti'l,.'C cl.CT.'SC:ifuptiu[I 0:[ ;'Strong ion sO]UJtiO[lS is O[)~y s.lHghtly more oomp]icatecitb.a:n that for ptl:re 'Amte.1f.

H'dl!t::}! did not CQn~~hl C01:' sea wa~et'andunl-efSd~u~~ flu~d VlOuld pfQ~ude two 'bidogk~Uy impott1lfiil c%:amp.b, of 5uc~ ~troflg inn. sO]I[]t:ion5. Their CO~ cU[lt:c:rttGD111Ipl.i.C'.lLtc5 thdr be.~1Ivioit, however, so we shall rJot:arJa~yze them until Ch3p~er 6. Inthe mea!:ntifi'il.e, t~eitd.at~vclr s~.mp]e ana]y"s~s of~h]s chapter will previdean essen~]al ba:s~s for l~a~: more complex one and, ]ndeed, l11~keDtpos:~:Ub~.e,

Cunside.iffirst a simpk solution made: up by ~ddi[lg ~p;c,dtkd 1I1u(m:mlItS ofNIIOH and Hel to \wteit 5D thst it contains only Nca .... , CI-,. 01-]-, and H ", [N a"'] and [CI-] are known G1uafliliil]cS" Gwen. them, horw can we predict [H'] and I[Oll]?

T11.i5 is II. ty:pim~ physks p:ttoH.cl11. '\X,le:: have two u[lkn.ow1!i5, [Hf]] 1I.nd.I[OH:-],. so that we must be able ro write two, hut normore than rwo, simu~t:;tn.eousllyva~.~d bm ~.f.'II.cl.epe.[ld.emqu,al'IIdta~ive relarionships between tflefil. Chapters 2 and :3 providethem imfiled:iarcl'y.

T11C constrainr of clectrieal ncnttalityrcquircs that

[NI;;l]1 [eil] [HI] (OHr]I=O

\Ve have OU[~"'IO eqeations in t\'\1'0 unknowns and can solve them e:asilyby the scameproce~ dure we used in Cha~Jcer 3·.

Ifwe use (4.2.2) to substitute K"Q/[H~]I far [OR] in (4.2.1 jandclear of [!iI!c~iarasj the result

[H f nONa]1 [ell 1) [H+] K'w 0

(4.,.23)

[OH .~~ UNa]1 [eil U [Orn K"w o

(4.2A)

ilf A:X? BX C (I tlhei!'! X

J """.. ".. B

1 """'" '" '2A.

UNa] [el n2 (IDNaJI ~CII J)

.~ 2

(4 .. 2 .. 5)

IH

OIH

I' ...... f'.w

{IONa]1 [ell ])2 4

([rliJa] I[CI]) 2

(4.2.6)

EquaJtioilis (4.2.5) and (4.2.6) solve the problenl!Given an}T vaMues for [Na'] and let] in an "N!J!O':' sQl.uti,on, we ~a[lc!J!lculjlte~he v:dues tb.liL~ [.1':-]-1]] !J!.nd.I[OH:-] .I:m,]s~ ha!"l~ If'rcOln these eg'lla~ dons.

These equations tell us d:mt we ha:veabo solved the more pe:nd probJem. The serong

~(lI[I '()Qt1()~nti"ti(ll[ls en~ej~ ·ail.~. theseequsticns on~y in terms of the dUfe:fl;nce be~wee[l the' tm!J!J Sot[)ortg c:aJti.on. lIrtd rn[al S[to[lg anion. ·co:rl:ccf]rr:rndo[l&. Th.us" in. t:h b 8hllP~C sO~jUJtio[l, lEwc: weteto ~[IIcre:ase both [Na"] arid. [CI.-] !by the sarne amount, so thattheir differencewas ura.cJIJn_ged., (4 ... 5) and (4.6) tell us thm: [H"] and [OI-l]]\VOuld 01]00 be unchanged, That would correspond toadd-

I[CHAPTER 4 - Sl1~OrllG fuMlS ;'J\lll} liHiE Si"ROMiG [01\1 [)~RfEI[l;EI'KED

[.57)

ing "neurral s;1h~," NaG" eoehe solution, (For si.IIl~)]icit:y,we igtwre :for the moment ;1:l:11yeff'et::ts that~he ini;~",~s~d m;lnQ~.adty 11ilight h;J.ve 01] tbe value of K' 'if[J, It follo'\ws th!l!!t i.fw", weee wadd. other stm[lg ions, such as [C, .Mff+·, 80'11-. etc, the only i;h;l(]ge in the ~hove eq~;lido(]s\!i'ould 'be thatthe term ([Na"~ - [leI]), wheteveric m::,cI[]:rS wouldbe espanded to ([Na"][ + [K'"] + [Mi4-~ + [u~+l] - [0-] - ][SO;~-]et:c).

.. ....,,' .

Eg;ul!lti.on~s (4,2.5) :.lI:nd (4.2.6) gppropci,;[frdy e:xpmtdcd enilglh~~ us to ptcdid[h~ [H+] and [[OH.J velues :[o:t an}' M;liLiltiilnc:~lrtt3in~ng Unil.~r st[;ong inns. lPhpk:aHy, this sl[]:rp'.t.~s;~ng ~hup~.i,dt.yre- 5U~:t:> from the fact that because sl:[:o:ng ions arenot invo]\l.(,:d. ~.f.'II J:ny chemical reactions .1:[1;. the wh.Mion. a]]~hat matters ]s, the sign of theirelecmeal charge and how rnw::h of it there ]8. 'The exP.IJeSSIOfl ([N;;t] - [[OJ[) can ther-efr.llr-e be seenas ~.m~as~t:e Clf~h~ n~iI; p05ud"'~~~ei;t[uc:a~ d1al:ge in. the s.ulil]JtifJ:nil.d;ru: tothe p:tcSCnila: ~_lf th~ strong inns Na'" :.lI:nd CL Eleci::dc:a.~ :[Icmtality requires that C.hll:fgt: robe ceunterbalanced lby the net negative dec~dcJl charge suppliedby [0[-]-]]

- [J-:[']. That is just whll:~Eg\.u!.tiioo (4.2.]) says. Equations (4.2.5) and. (4.2.6) thentell us how this~quir~tl1e(])l; InUCSl be nwu so tha~ wate~ dtssodadon equiUbrlUln isalso satisfied, gjv~n !I!.tly spc:dhcva~.llC:s fot [Na"] god [CI-] (~md K'w)' T1JJ~: sp~dHc:~dcniltity of the sttt"mig~Dns doesnor entes the <'Ltg!] ment; it is the net amount of stm.ng ion po!S:it:lve electrical (:ha[ge~ha~ determines (Equarion (4 .. 2.l)11:ppropr]a~rlYexpatlded) how large the [OH-]] - [H;"~ d]iference must: he.

41.31iHiE sTh,oiNtii roNi iIlIFFIEfl:iENCE {SID)

'T'h~~o.ng S~:I:'ung of 5yh1bo~,$ expt."l;ss~ng the net s~ro[lgh[l PO'$~il;~W charg~ wh~n :In!l!ny differ· em: :$~:Jo.ede.$ of :$~:I:'o[lg b1S lI!n::present in ;I 5d~iJdQ[li8 cumbersome ro write a~l~~[:Jo.eatt:dly. Itis both itypogr:;ltph i.G1lHr andcoaceptually convenienr to GI:1l .it dl~: 5tWng ion di.ffi::;ifertc:~,. [S[D].

Dennit.iOiJI. The :str-Q(]g ~.o[l d.ifft;ft;I1i;e, [SID], un any s.oh;wd.o[lis d~l~ned as (th~ :sum of all th~ sJuongbasc: cad~lrt ClDnG~lJtrnt:iDns)n(linus (i:h~ sl[]:m of :aU dl~ st.wliIg add! anion oonceetretiol.ns); allespsessed jn eqldvalel.lJts pelf Liter.

Out s)'"St:cru.l.-d!~A:ning ogjUJd~IDS mo't soluEnonsof SEl'Un:g d,ec:t:t{1ly[~5 i!Il'.lly thenbe :~tkt:c,n more compactly in terms of [:5[D]] ri:htls~

[SlID] [OH] 1[111] 0

(41.3.3)

--r.l:lJealgebt:iJJk sohuions to tbeseare, fromthe previous section,

1[58]

[SHl] J 'I .2

[SID] ) 2

[B ]

[O~ ]

[51 ID] :2 [SlID]

l 2: ~ 2:

(4.3 .. 5)

Jn a fO!l::l11al sense, our goal has been r~(;he,dl, Eqilladons (4,3J), (4.3A), ~nd (43. 5) so~e~he p:[uHen(l. Gi'l,"eI1l. d1C: str'Ong ion camposi'[imll ~lf any ~O~llti.o11l that contains on~y sttung dcctto.~ytes, we can 9!ri: once calculare the [f[~.l and [OFq of thatsolution [rom~hese equadons. Th is dry ::;!:a~,efi'i),em ohhematbematUcal resu]~ does no~ go. veiT far~o oLO[liVer thepowerfsl generality-and understanding ]mpli(:]~ in these equa(]oos. '1['0 do (i1a~:, we need. to examine Wh:M: these eguadurts sa~1 fl:1.)ll1 ~. nlumbeil: .of d~ffl;fe[l!;rer.Sp'ec:dvt;5. \'qr; :shaH then havr;amotl; t:homll.l!gh bl.~~b ff)'r the 111'OtC c'OiJtlp.lk:llltodi :.lI:I1I."il~y<~cs. :tt"iJuittcl when. so]ut:bns also conltail1l.wc:ll:k. dcotrdytcs, JlS well JlS COt.

Cle!1d.y,negat~.ve values :fO!l:: i[ld~vndual ~Ol] ii;o[l(;en~~jdO[l5 have no physical. i11ean.ing, bUll; the value 'Of [S[D] may ·bi:[Icg:llt:uv:c:,. zero, orpositive, dc:pcnding un.. w.~cthcr 5~ro:[Ig acid :lI:[I:nons ott' strongbase caldo[ls Or neither aI.Ie in escess .. The acid-base behaiviot of sclations is :mqJ:risingJy di:ffelJen~ inthese three o$ituations, and ]~ is esseneial to uilderstand those diffelJences. We mam eN:aln~:n..; dl~l11~n dJ~t~il.il] t:~e n~t fr.;w ;ir.;G~.O()I).s,

In. biD]ogjcal rolml.ons, I[SJD~isalmo5t J1\v:ays Po:lJ.tU-"e. In. mamm.al.ia.n. boclyfluicl;s" .it I;S on. tfueorder of +40 mEq!iLi~er (OJJ4 Eq/Litet), In. estracellular ffuids, Na+ and. CJ are the maior 5tiEOng iorrs ljl~sel1Jt> and [S[D]is l1Jo!~m~.ny clo.sr.;~o ([N~+] ~ Iftl]). [nJti"cdlul~dy, 1<:+' and Mif:liD: themajor stl:{llllg .i.u[ls, let] h 11;."l[]aHr small, :.1I:1lId. [SJD]I L" :.ltppmxin(latdy ([[("]1 40 I[Mi~][).

Un,tH the [SID][ljm~donfulec:omes (-amil.iar, :u~ 111~r hdp Ih,e~adJr.;f tQ~pb.ce [51])] by ([Na+] -[CI']) in dl~nkingibo~~ t~(; Inea:n:~ng of eCUL,l~·t:iQ.11sand gl"phs Of W~e[Lr;y.(;~ [SUJ] an':l}J@.l:s .in t:he fullow.ing diiscll:.''l5JOn.

4.4 SMIAU. [SJDJ VIAl!..UES·: NEUTRJil!.,SA.l!.T SCH.!UT.1DNS

T11.e solutions for Etlua~b:"l5 (4.3..4) and (4.3..5) fur vJI]nes of I[SID] ranging from ·-l~J"~o-+ UJ" Bq/Lirer are displayed .illFigu.re 4.1. "Small" for lSID] means "'values dose 1'0 K' ,t. This [ollows friJln the form of ~~e eR~:Jir-e$sion ~n~skl,e the sqUiar-emot ~n Eguadon:s (4.3.4) and ('U5).

WI:l:enevet (I[SID~ /2fb, much .~.a[get than K.' ""f~ then. the value of JO< 'w ([~SIID] llf) is veryclose to [SJDJ/2:. K'~. is 'On. the utdc;t of 10.14 (Eq/Uitct)2,. s.oJK 'w b 0.111. the maier o.f Ml' Eq/ Liter. and smJll [5.]D]1 means less than. abm.1Jt W·~ E~IUtet. [5]D] in bod)' fl.uld~.by compariSO]]. is gene:r:aUy larger than 0.02 Eq/Liter,

Wh.en. [S[]J]I is small lby~hi5 u.D~et.r.on,an.db negative Oeh halfcfFlgure 4J}, [T-!I"]I is a.I.v.rarys,

I[CH ..... PTER. 4 - S-mOHG roNiS Al\IID' THiE SiOOM:G[ON D~RFEREM',CE]

1[59]

F9 + :rr:

......

8.011:-7

1L,OIE-6

"J::J

s 4.0IE-1

IFiigut'e4.1., [~I'~ and [OIH-] YeIt'S'l.I:S I[S1O] iin, s<oluticm or :strong iion's; wii~hi I[S1O] values smaller thain, 10.6 Eq/lLloo!r .. 1<:'1.0' '" 10.14 {IEq!L1lter)",.so, I:ltl!at. wiM,eri1! [SID] '" 0, [H+~ '" [OH"] '" .jfl\; '" 10.7 5q[/LJItel~" These curves de:scribe: t~l,e: acid-base belhiavio:r ofalrny s<oluticm (;(lnitaining only :stnmgl i:ons, over this 1[:5m~ range.

largc[Ehan [Oll~>"vhkh Is h1l!tt'dly ... :>u[p[L"c"ix[1l!l[]5e rlcgaEhrc [SJD] means strong m:idi CXD:Cch strong base, Wha~ is sutp.d;si:ilig.a~ first isthe difle[Jence betweenthe [H'jandthe ItOfl] curves" [H+j varies ]iitlear~.}' W]tll IlSID~ oneethe magitli'~ooe of [Sf]]] is above a'bou~ 10-7 Eq!Li.t:et. Wh';;[~!l I[OB>] Vjlj:ii~$ i[l.!ll ~~fVH~:I]~jll: f!l!s.hion,;il.nd "'h")I~!ll.fS 1;Q;il.sytnl:ltQW row,;[;d Z~1fQ ",$ [SID] bCCO:lllCS .inc.lC'iiI.:.'li:ra~yncgatUvc,

When [5]D]1 is ,exactly zerc.atrue neutral <'s<ll](sDlu~ioitl," then we should lind [fl1 == [0[-1]1 ;:;; K' 'fill' and this is indeed the O!;ac~:r.;, The l[r-]~] ~tld [OI-]-]cmrves intersect just at [5]D] ;;;; O.

W~en [5]D]1 is positive, cotrespoilidi.[lg. to ~. small escess of Strong base over st[Jong acid, tben.I[I-Ji] <lind IlOJ-:[-]1J1ay oppesire roles eothose desezibedabove Now fOB'] varies Iinearly wj~h [SID] Q[lO!;e [SID] is l;il.rg~r d1J~t1 i"Q!.,I~ 10-1 E~TI...irelt'>~"ibeif~!llS. [H+] vari~s nQn~~:n~dy, ,;nd. app['O!iI.G~es tt[;O iii:> [S[:D]i[lctta,~:>"\l'hC::[Iev.ctt' I[SID~i:> pD:>Jr.Uvc,.I[OR] is l1i!ttgctt' th1l!:r1 I[H4],. as expected,

Ag~lt'e 4.1 detnQ[l5tmn:s all th~5e points, bu~ut may be he~pf~1 to look ~.~ 'SO:l11~$ped~i,c numericsd valnes. It is ~looi['l6:JItt'lnat~vc to pUot the :ttSU]ES o:f these ealculatiens 011 Figutc~U.

[60]1

Consider fir,st'il dilu~e"NlliC]'" solation with ail inieial I[SID~ value of-·].O'x l(J7Eq/lLiter. 11I]S v;;I,il.~m~~ns dl~l; [CI-]~5 1()c-7 ECJjT~;t?rl!l!r~~r. il;ilan. [N~+], AS51.m1ing 25 QC, SQ thlI~ [(' w;;;; 1,(:1 X t{)-i.~ (lEq/Llrer.)l, ""'" ca[l use Eqruadons (4...:3.4) :and (4,3.5) to caleulate dle v:a~ues .in dlel!it'5~ rQw of theltio'lbk below; Whgt happens if wc,[I:(}w add 1.1) XW-7 Eg/Litet of HU. tnthis solultbn? [SID~unc:reaSJes (rat:g:ll!dvely}w, -2.0 X '10-7 Etl!U~et,and~he otht::I."\laJh:~es dlalt1ge as .i:lrld.ka.red

00 t~e eable, 'These resw.lts should lJeexlliminedi carefw]y to see how they differ from intuitive expectadon~$, No OH-"",!!!s ;I,Jded Qrl:l;i1lCl"l~d" 'fu,II,J!f; [[OT-l] decr~s~d by .34%,. 1{)-' 'E-q!L~ter of H+ was io'Iddcd, but [B"] o[l:lriOlc[C:ilzdby 7.9 xW-il Eq/Ut:c;r.

Originalll So!JLliti:Ciifii Amount ,Add~d fl nal \ttl I ue Ch;:!ln.ge

[5]:0]

-1.0 ~>i 1:0-7 ,,;1,,(J':x 1:(J'-'

-1 .. '0' X il!O-7

[IHt]1

pHi

:Il.6 x :IlO-~ l,ij x: lij-~ .:2.4 x ]0'7

6",79

6.,.62 -0..1;8.

<1i- • .2 X to-A -2,,] x il!O'-H

+7,9 X!O-H

As it second. esample, on the oeher side of [SfD] == 0', imagine adding the same illUOWU of HC~ K) ~. dUUl,l!l"I;e "NaCl~' C$oIl,ldon in wlh~ch [SID]~s ;:niil;hdUy + 2,0% 10-' ECJ/T_J~er, Inthiscase, as dl~ fo.llow~nglmhlc, ind:~cio'ltdl, [[DH -J fills by 54%, a~dli1Ugh we stj]] hmvelllfJlIt :addod otrc,ni])tJv~d. aJlt1y OB.-., while [H'"] risesby Q.1rI]Y 41'% of theameunt of H" added ...

[IH']1

[OH']

Origin;:!111 SQlll,!Iti:onl Amount ,Added

Fi nail Va I ue ChaJt'I.g·r:::

+2 . .0)( 10-7 ";1,0:x l!O,-7

"ii'l.O X}!(jJ·7 ";1,0:x 1:(J1-'

41.0 ]( ]O-~ un x ]Q-7 6.,2. X 1!O,-R ""'2,1 X lO~>!!

7.38

2.4 :x 1.0-7

7A::ils ~0.33

].6 x ]O'~ "{,9' x lO-y

In neither of these examples does the dn:nge .i:IrI.I[H"]lbea.ta, simple, obviousrelationshjp

[0 the amoum of H+ llidded,. Even more su:,]kin.j5.I[OH-] changes by wmpar:abJean10unts,e".'en t:fuough [to Ofl\\ll1JS added or removed .. Ifwe had added NaOH instead of Hn. the appos~te would have OCCUl.'n::d.,: [OB"] W{)uld haVl;im;l:l;a$~d !lind [[H+] WQu~d have d~cl:e$$~d, even d10ugh no H' \.VlJ8 [:rnmlet.[Cd~mo Ol[ om of the solurinn, The only sio'Ifc, guides to pttdkdng g:OIciI. underst:H'l.ding what Inppe:ns to [H'jand [Ofl~in~hese sku:;ttiolnsa.te Eq,uariaos (4.3.4) a:i1id. (4.3.c5)

or the curves .of F]£jll.ll"e 4. L There is, however, one useful generalrule from all (1I]S, whenever [SID] chaoges~n~h~ :[I"'~il;i.ve direct~Q:11 (1um" str'l)ng ~.cid or.les$ c$t;rcQog ba;$i). then. [1':-]+] increases and [[OH-~ decreases, \When~VI::[ [[SID) ch'il:nblC'l~n the mO![C posili:we dirc:cltion, [Ofl~ i:[lcre:::a:ses, aJnd.I[Ff'] decreases, It is also n.o~e"rort:hr~haJt when [5]D]1 ispositivethe change in. [H'] isd'il,rays much lessthan the chllinge ]]] I[SID~,. [1:1 ordereo be useful.ehis general rule muse

[61J

"t::l

tij4.011:;"'4 -

O.OE+O +- -----'IC---,r------T"'""- ... :;....--:r---- ....... t..:r-----""""! -1.OE-3

-,6.0E-4 -2; .OE-4 0 ,2.0 E-4 6.0 E-4

Str'ong Ton iDliff@renc!!! .. SID (EQ!I)

r, O>E- 3

IFiig~!I"e4.2. [!~~]~In!d [O~q V~1f51!J1S [SII!)] iln! sQluti,on of 5tr'Q:n!g lions WiU!1 [SII!)] values up W l,(I-3 l~l::Il!Li~r:. CQmp'~re with "'igur~ 4J" wh,~ch, m~y b~ 5ee!')~s <.'!i!')tl!n!~rgelT],tiilnt Q'(the Iftiil.glio:n! d!oseoo (Sm] '" 0, The IT]lost iln!'lPQrt~nt~~~tl!Jlll'e of this fiig'!.!!re iis; its clear deIT];o~]s;l:br~~io:n! th,~t chl~ng~s in [H~]are rl!ot !lllqlU!al to cha!t1l.ges lin I[S]:D] when [S[iD]llis positive, iK'!,f/ Cl :m-'1'! (Eq!Lilte~y

besepplemented brl1lUl11t:1[ica] calcalations 115 was done above, Bquations (.!J+,.3.4)anrl (4.3,.5)have aJ:le~HT:l1O .• d]na:lt']hY ]mporm:l:lit~ consequence d~a~: has been i.lllp]i::~~ inthe above d]scuss~on butmU!5t be tJlJQ!mllgh~~rll,l!ndeffiWQd. Tha~u5. becausethe val,l,ll,e of [SID] d)etel:inin~s the ~11l,l!e5 of [[_]4] gnd [OB-] in. thC5-<: solutions, o(Jh~cn':.u:ion fyf a ch;,tf.ilgc in [H"'] can u[I]r mean thai! [SID] has dl.angocl. Me:as!llfocll[I-t]1 chJnges. [;11:[1. tell U3 nothing about wbethertbere has been M)' ~r:ans['el of H" .into O.L > om: ofrhe solutionjthey onlytell us tha~ strong ions have been added O.L ~Im}v.ed so a.c$~O ch~nge [SID].

Wht;n~he exC.~S$ of ,s;~ml1Jg lldd anions OVi;~ Sii;l:Qng base 'C:~ltions ~$~~rge:~ than ~IOOll,l!tW·j\ Eq/Likt, Eql[]grimJi {4.3.4) 5im[J.~ifiics to

I[SID]I

(4.5,1)

[62J

. :U:Ie-~

Fiig!l.Ilre4.l. LQg-log plQ1ts. Qf [!HI"] .,.nd !COlHo] VeF;!jl,l~ [8mJ iiUlI5iol!J,JlbiOlrn Gontaiilrn~lrng only:stlrong iom; (pll!J,JIS W and OIH - ~) QVelFa wide I[SIDJ r.alrnge. The~.tr;:llug!ht line M.rhe~UlI [SID] is 1;:Ilrg:er then 1(1-7 Eq!/L reflect the <:Ilpproximations tJrnat [OU] = [8[ID]1 <:Im;!1 [IH <-] = IK'"", / [8m]!. For ne;g.atiive [SI[)] \!'<:Illl,Ie~, IJrney relilect [!HI+] = - I[SID] end [O!HI-] = IK' ..... J -[SliD].. K'w = LOx 10-],1 (IEq/IL,)2:.

EqU!~Ji;iQ[I (43.5) b-"'CO:llleSu~I~5'S under dl~S>e dr~il1;$tam:;es and il1r;15r;ly tens U;$th~t [OH-]i5 elnse to zero. EG)Llar.n(Jn (4 .. 1J} 3.I.QDligW.ir.h. {4\.5J) abeve is !1(m:oc hdpfll~. and results .i:Dli.

[0&1 ]

(4.5.2)

Equ~lI;iQ[lS (4,5;1) !lind (43.:2) tellus hO'W [H+]andl [0]'-1] 'behal'lleutl ,stwrngadd ,soJudorns, whiehmeens Sn]ultiDns whh [note: suong 3.cH anjotrsthan sti:nlilg base cations, snithOlt I[SID]n5. [J'cg:J.ti.'1lC, Such sulilll!tiQDliS are :rn:rc in b.blogka~. systems.

The be~::I;ilViQr proedkwd by dl~5le~'Q equ!~lI;iQ[I::i is Si.j1.1P~~, but dI:uflkulrt 00 v.i~1.1~:lize: gt'!l!p:h:~a cOIlIr on linear scales, Figure 4.:2 shewsthis iDli k,o; ]dt ha~.f>whe[:e [l-[~]I follows a 4S' su'l!ight line, and [0[-]-] Jstoo small to be seen. The Jog-log plots of Figute 4\,J are more useful. Tile Ieft half ofehis figui!je shows (;hrecdy~h~t: I[Fr] is equal L'O the magnitude of [S]DlIWihil.e [OH] is inverscly proportion~lto [SfD],. I~ also shows that as [SlDllbe(;omes very sm~]l,. [HI] and [OI-[j

I[O-tAPTER 4 - SrnorliG IDtllS Al\!li} ,tiE $iIitOWS[ON D~RFE!'!:EMlCEm

[53)

both ~n}proach the (]r.;u~ml value of JI<. """, . ]tus ~:~50 110teworii;hy frot11 Equ;lJdo[l (45J)~ha~ under these ·aonditbns 0:[ ci::%l3e.~S st~ong gf:.~d, [H+] .i5 inde;p.ellldenit of K' w' but [01-1] d~:peillds directly em K' 'If'

4.6 [SID] POS.If.IVE AND U.11l<iIER.flHANlIl.O"~ IEQ'/ LIfr~1I:

When [5]D]] is positive a:l'lld .. largerehan ]~Jf., Eq/Lieer, corresponding tD a s.ig;nifica:l'll~exce.ss of stfi)ng b.il'$r.;o;;~tiot1s ovr.;:~ stl:i)ng ;I,cManio(]~$~n~h" '$Qlu~.ton, :E-q~;ltio(] (4..3.S) 5hnp~.i~~~'$ to

[OB] [5W]

(41.6.1)

(4.6.,2)

The rlght-hand balves of'Figures 4.,;2 and 4.,3 depict what theseequations say. [01-]-] varies dicecdy with [SIDJ while [H"] ]8 yery sma]l and. Vlliries inversely w]~h [SIDJ. As [5]D]] a~jlproacb-

es ttlo"'() [t:01n positivI: values, both [H+] and [01-:l-] gpp:OCIach ,JK"'l1 as thl:Y must. [H+~ d!c:;pe,nds directly em K' 'lIP [OH-~ does not,

Ausd\,J.~.v:nr;w Qif th~ w.~~e ofEql,l!~i~kl\[Is (4.6;~),. (4.6.2:). (4,5.1),.!lI,l)d (4.5,2) is prlJ'V:~dedby~h" tbU:lJw.i:[Ig simple; example, In(l<lg:inc~ha~ \\'1: have 750mL of <Ii to xl(]C"~ N "N<l.OH" solution <I:n:d. that we add 250' fi1I.L ofa 1.0 x w-~ «Her' solution .. We shoeldlike emf equations to bell 1]:5 the [H+'~, [0[;;1-]] and ~)H 'I!~!'ues in a]l~hree of d1iese solutions. To com:p~re results w~~ih the ~amples above :;l[ldwuth Pigu~ 4.l~h~Qugh 4.4,. we assume K'w;:::; LOx 10-14 {Eg/Litei)'~ thiICQl,JI.gho~t. "I"hl: DI.[.~gi:n."ilI. "N<l.OH" solucioa c~);mgi:[Is Na.-+ butnn CI.- > 5,0 .its [5.]D]1 ;:::; [N a+].,. Shlli.~.'i1lt~y the lld.ded. "I-[e]" sohuion has Cl but no. Na -; 1lJ:n1Id. its [S.ID~ = - [CI.-_]" The final '1 Luter o.fmi},')ed WlUl~ioIDI. contains 0.75 x W-·~ Eq of N ~~ ant] 0.25 x HJ~' Eq of Cl' so' [h,ll:~ its lSID_] value is -t O.5{1 x~O-~~ Eg/L~tt;[. Appnyung the apipfOpl:'ia~r.;t;guatiol)$,. we cal) th,er-,efnr-.e easUy fum un. the fn~~al\.vjng quami~atuvc:; d~scdpt.nDn of the sO:IiU!tin[ls bd6t""c :.1I:n.d! <I.[tl:;[ m~:x ing::

SU!l:ist.a!f'iiCe 'Ol! Qml!liIittilty

Amount ~n 'orlgllf1a!11 ~NaOW 301ution (I~(O

Amoul'ilt In added ~hlCil ~ sO~!l~tiolil! (~ql)

1J:ota!~ .a meunt CiD!f'iiCefltraUon

added to' mixture In '1'1 nail mlxllLIre

{I~q) (I~q!~il:er}

INa"

7.5>1 1O-~ a

o

2.5x· 1[1-4

7.5 x 10-< 2.5:x 1,0-4

7.5 ]( ]0-4 2.5 X 1:0'-4 +5 X ]O'~ 2.0 x lo-n 5.0 X 10-'<: ][0.,,7

CII" sto JH+ oa IPIH

7.5 X 10,12 7.S X 10-4 U.O

2:.5xW-~ 2.,$ X 1O-[~ a,o

2:.5:x W-~ 7 . .5 X W-.t!

1.2. -

8

.2

O+---------~------~~--~--~--------~--------~

,1.()I!;,3

FigIUlre4,,4.1itral:i:on curveror SbOIil.gl i~)n soll'l.ll:iiom, wiitihl K'W .. 1.0 ")( :m~n.4 (IEq/I,)2. IPlri p,I'oUed afF~~lrnSil: [SlID] overtthesame r.ange as In FlglurB .... 2. This plH 'CllJlrve Is 'tJhlern-afisform oUIM,e [1H']1 GurV'e~ iilili Fi:91~Jlre~ 4".2, by means of eq[UlOltiiolill 3.3.1. l<"w"'LO"){ lO,lA (Eq/~"jtelr)lI.

Thisexample is deceptively simple once: EqiilllltinlJJis (~.6.1) ,.:m~. (4.6.2) have: been cstabllshed.

Itcl,e:a~.y shows thatneitberebe ch~t[lJtb-':t JIl. [[FI1 (from UJ 'l{ W-It in the ol:'u,ginal NaOF·I solnsion to 2..0 x ~O-IL ill the 6nal mixwre, a d:"iange of Ul x UO-II Eq/Lieer) ThOi" the 6na] value of [[Oft] bt,..">lf5 ~ny obvbl,];s 's~tnp]~[-dat~o[l5h~p tQ~hr; llhlQI,l.n~ or H-I ~ddir;d, 2,5x~O-4 Eg;,l,l.lJdir;e t.hr;5~ (3oln·d:~drn15. ~.lfpBS~[hle [SiD] values inboth the:ilJJiuti,.] and tinalsoletinas,

Fma]]r. ]~ shouldbe no~w~ha~: under these condieions of positive [SID] the value of [H+~ depends di[ecdy Q[I. dle vslue of :R'1l)' as EC(fI,l.s-!uon (4.<;'2) shows, so k ~$ ~sse[ldallQ use thea-p'" p:~:Up:ifJate:: value: ff_U in such l[all[llla[jorJ~".

4.7 [piH CI.!IRVI!:S., TITRAliION A[N[D· Nl!l!JifRAUZAnON[

The pH tr:a.IlSfOlft.llaJdo[l.of '~ihe [H"] versus [SIDI CU1fV'e in. Fugm,e 4,.2 is displayed in Hg~ue 404 and should be rai!:1ll1:ia:r aswiha~ ]:5 l.!SI.lJa]lY cal[.ecla"t:itn~jjon"cu.rve. [t~ is often presented as l'esu~ti:l]g fl:"Ol11 tlae :ildd:u~~on of successive sl.llaUa1nQ~,mts or b.a$e, such ~s '''N>lOH':',. to II S~ft);[Ig acid sclution, .i:lJJi. whkh ClISe:: the::cu[vc: is traeed from theleft sick toward the:: center, ~lif as the result ofaddition ofacidto al :>I:[Ollg base so1LutUci'n,. ~.f.'II. \'!ihkIt case the ~UI1.1'e istraced from the

I[CIHAPTER. 4 - Sl111l0NG WNlS AI';,Ili} liHiE SilWNiS[Orei DIRFERENlCE]

[65)

[SIID]1

I[W]

m:me a.on

0.031 0.020

:L~2 X 1l0·d2 2.20 x W'IZ 4A{'1 X 1.0-!2 2.]Oxl0-7 0,010 ucco

o.o:n 0.02 0.1)]

n:9 n.7 n,,.

6.58 2.00 1.70

0,010

a.mo 0,0]0 a.,o:m

0.00

2.10 X W-7 4A() X ]O-l~ 2 •. 20 X 1O<1!~

·O,()W ·0.020

hlblle 4.1. Tiit!l~tion .of C:02~f!J1fi!~ tissue filuiidL AlllloonOflliri!t!l~tions un, Eql!ILit:@!I.ComIPositi:on: l[tI.I~"] a.B/t [n] ().11l; [O~'iI"] OJ]]]; I[Kt] o.mJl3; [IM~ft]1 0,002.; [Ca2-t] 0,00].; [SO}-] o.uoi: [1"11"'] 1.42 X 1O-!2. l1::'w:::l4.<11 X In-!A {Eq/lLiter)2.

right: side t:owl1Jul~he cente[,When. t:itn~ion is '\::omplete", ~]l the acid. hasbeen <1:iem:rnlized'" by ;I,d,ded base; ot: viee V!;;tli;l,~hr.;${jlu~k)l) h~5 [51 D] :;;;; 0., and pH :;;;; IlK:' ;;_!,j2 ;lIt the cer.llter l.wi:IJIlt

of d~e curve. Th is cerresponds 1'0 (he I[SID~ = 0, I[Fr] = I[OH-] = .JK '.,.,. upoi]]t· in Figure 4.l

This «'JH[itl:'atiofll." cl[]:rve;is verv useful in.. ·p-'.I:'a!Ctk:e::bocause tbelanse and :ttJlItive;lv abrupt

t f~.. Q ,{

pH cha:n.gt: thai! occursnear themeetral point is e;ws;~ly detected e:-Kperi:mentaJlyvtithco.nsidet-

able precision, It should be dear from ~heg;rapt d]a~: the ~n1(lW'll: of S(l"m~ ~cicl or basethat l1lUC$[ be ;I.dded toil csoh,ldon to blt'ung it to that 111;:011:f,>I 1'lo()~(]Il; L$il direct measure of the [SJD]I val. ue in. tile nrig;~n~l sdution.> Tn[I'atiun L~[hetdDte; an. i.Mponam '.lI:n.'.lllyt:k~~ technique fotme;~suriitg t:he I[SID~in.soll1t~n;s ofstfon.gions;. It is 3:0 e.asy to can]! Oltfr thait it isalso onen. perfom'led on more complex wlrnio.ns 611Ch as urine O[ blood plasma, Irs ]nterpret;M~on underthese c.o.n.d.idor.ls IS muchmoee wmplk'a~ed, as we s~a~~ c5'Jee In t~e (]ex~ dl;lpEer, It IS still ~. direct measere ufhow much [SID] hils mollx. d)g[lge:d to get t:~e: 50~l[]tkmmo ~. 5podAca [H-I+] bur k.~ 5iglJi~HC'ance in. terms of the ob:'igJna] acid-base status oftbe ori;gi:n;wlso.~u:~io[(. ea,n.. only be u:n.ae:fStOOa. ifthat oo.hJJtI.on's rompoliutuOinis ;weeurntdJy known ...

The dJiff~ten.ce.. .. bd\o'ill:en.. the; [1-]+] versus [SID~ curves ofHg;I[][e:s 4J. 4.2, and 43 ~nd. the: pH vel"St]s. [SITU] curve III FIgtue 4.4arecndom .. The rnpndpH dm:nge in the l'lle:nghbotlb.oodi of ~5n)] = I) has no. counterpart in ~:fue [H"] curves; i~: is a mat:fuemll~ica~ ar~]_ran resulting fromthe lla~d.cijil~l!:~ pmperdes of tile douHy nOfll~(]ar [H+]~o pH t:f;l:r.lsfot'l11~(:uon, Til" s)rmI1WUf1r libol,lu [SI])] :;;;; 0 of t~r.;pHcufVe is alsov!;;ry l11i,slead!ung, as IS the fQ:l':m ohhe pHcurw w~en [SID] i.~[(Je:g~dve:. l"hlit part of the pll c~rve tmgge:s.!5 dlilit as [5.]D]1 bccorncs more and ttr.mtcn.e:ggl:i.ve:, changes in [H'] become smaller.wheress in fact, as Hgutt 4.2 !l:k;w:Ifly shows, [H'] centinaesto eq]Ual - I[SID~~hroughmM: this tai:l:ge, so that chall.~s in [H"] a[ways equal changes in [SIDJ.Yolll ",",'Quid never gur.;ss that £r.o111 iChelef~ pordon of the pH Ciji['llr.;, Over:aII,~hoUl.gh i~i5 faI1~illar> :u~ seems de;~[ t~;l(jt the pH c~nr·e;i5 HJo:n.f:l:ptll~Uymy5i1:erjou5 and misleading .. :U[ g,djds :nothi[lg;~o our u:nde:l"S~J:ndnng of [H+] beh;w:vI.ar as a function of [SITU]. The Mog":.logplots of Figure 4 .. 3, on the other fu~nd, are much more easiill.y ]n~erp.~e~:e.d andtell the \V:hJ!)~e srory a~ a.glance,

~]"1 . ". ssof '..1l • '. ["ID·]· . '.,' "·1" ·1·I·d" ' . '·1' '''.' ae 'I-h .' '.1l b

. nc pn}Gc5;s o : [C;llIuclngp... ", to Ze::Ii:U 15 ~ .. 50 ca . e: u. neutra J2'Jng. . ... e e:XCCSS >Jcl.llI. oruase

in. the oolutij)in..is saidto benentralieed by the a.ddedstmi:'ll:g base or add .. Wbat: t:h:U3 means

Hi'

o.is /'

Na/

-- -- ---- -l~·'D -t- __ O_H_- _~

f~gIU!re4"S" 'Gambllegl,am f~r tlhlesol ultll~!rn desclf'libedl In Talblle 4. L C02 tree lili1iterstltllallrillulid. See Th!b,le 4, . .1~Oi numelf'lic<l!11 v<l!llu!E!!s.

is that the d.ect!fk::aJl charges on the a:dJdedsm.:')ng :~ons, afapp:fOprlate slg,n eaneel tile o.r~gi,l.'Ia~ excess chargt ,of 0IJlpOslte s.ign, sothat theadcled H+ {or OH-)ean combine with. ehe 0[-]" {or J-:[1Q!It',~gi:naUy [1r'esentW foun';',"~wr. '''NeL,l~:rcal:iza~iQn!'' ,[-ea'uy l11eans "rrQt:mil:lg Wa[l;l' fnHn .1':-]+

d 01' r-, "I' e . __ .l!' h "f ['C'1l'])'1 " ' ',," 't'll7lL " ce. tralized" h

<In ","1l <15 aresu r o:u, :lCU!~Clng tr e 1i:~ZC: 0, .w.ll. _ EO 7.1:;[0. W nsr ~<~ neurra .zc , I.S t , C; excess

elecrrkalcharge on s~ro,[lgnons" whichis JUSt what [S]DIII:1J.1Le:astues. Theacid-base nemrnHty ft!ondutUon" that [fJ:+'.l = [OB] = K' ,J2 can onl} be met if there i;sJi]o other :[I,el: i.ol.'l,k iLhaJrge ,1:[1 (:he sohl!ti.on.When ouly stwng ions are presel],(', d'uu iswhat [.81D] = 0 means,

The add~~$~ bd1Javrof' 9f~n~r;fMitiailtll,lid (IS.f/)in viV'Q d~1~[Ids s~:It'Q[I~y Q[I.ircs CO2 II;;Q[lret11; <IS well <IS 0[1. irs [&FD] aswe sliall t;CC~[1 Chaptct6. KSfcan sdll p[;()ov:1de; an inrrctc5ting: exemple fo[~his ::;tage of ouranalysis if we nonetheless remove the CO~ from it .. A samlP~e of [Sf with ~H the QO~ removed isa veryalka]]t'!.e sclurion, in which the ma~O'.reons~:i~:!len~sb}' f~:r, Na+ and. 0-, a[>e 'set ~t quite diffelfe[lt ·cQl1centlfatkll[lS, ]ts 1[1':-]-1] is '~Ax 10-12 Eg/[;u~u,. [~B 11.9. Iss de~;lUlr;od ~ompositi.on. is mStoo ,j;[I. T<lbl,.:, .ott

The resldts of t:ill"IMing U Lieer of (lI]s solntioa byadding successive a~i.qoolis ofHCJare also

[67J

listed in ''j[:able 4.1. Because theill:itia] [SIDJVllJ]ue is 0.031 Eq/Liter, we ha:ve made the first HG addndon 0.011 's~.tn~:l~r~o bring [SID] lOS :(1)qJ!nd number, (U)2 Eq!Lh;~:r. Suc'Cessive addutlo:n.s a~ ~II 0.01 Eq .of Hel. Asr;N::~'l<ecocd, d~e [H+] and pH valuesjnthis table H~ .on curves sil11~~:a1: mthose in Hgu:tcs 4.3 and 4.4, but not idciDdcal. mthembeceuse [SF 113$ a different K' "IIi value than was used for those figures,

Inurriil1!lly, [SID] is large and positive, so that [01-]-] ;::;; [SID] ;::;; oJ:m Eg/Litet and [H+] ;:::; K'Il/[S]D] ;::;; '],42 XW·12 E.Cj/Liter. These values are .Hs[ea. in the first .[juw ofTable 4J.l.lllbded "'Ii]olo,e" for .itOHC1a.d!d:~tnQl.n.

Addinllg thc:f1.rnt 0.£H1 Eq!Uter of He] .&i3s[he cffi::ct of lowctit!!g [[SID] ito "'" 0.020' Eq/Lker, so [OH-~ also faJ~;s~o this v,)!]ne, [H'j rlses bra. mi:n~$cnle JimOUIi]!t,

The 'S~CQnd HClail.Jquot ofO,(n. 'Eq/Liter.~ower.$ [[SID] K) -} 0.01 Eg/L~.te~, whh;:h is 'st;iU large and posirivc, So [[OH-] becomes 0.01 Eq/Litcit, and [1-[+][ agil1!~iD rjses br amdnlscule afi'lO'[tIi]Jt,

Thethird HCI!ldd~tloH reduces [SID] R) ze['Oal:ld~~~ls us, if~· had no~known h odginaHy. that [5]D][ it!!. the O:ifigina1 ~a[lnp~e was + 0'.031 E.q/ Liter. [Ofl'] f3Hs, 3nl1a [H+]riscs,. to the add." base neutral value of JK "'II , {)!r' 2,1 x ·.~.O; ~ Eq/ljter (pH 6,,68,. not 7Jl!).

The fourth and iif~h HC~ a.dclit~on.s carry us' well beyondacid-base neutrality .ifltD the negative lSID] regioa, 00 that now [H+] = - [SJD~ a:l'l.d [0[-111 is minieeule, [H'] increasesby ~J.Ol Eg/LJtr;t' wkh each Hel addidon,

This table also pw\'icles an example o.hhe serangebehavior ofehe [H"] eo pH transform.

Colll.pa~ t:h~changes be:~~en th~ semnd and ~hi[-;dIW'Ws, and i;be f~fth and sbnhr.ovro, Inbo~h GlSCS, [S[ D] fa~t5 lbr n.,:QJ1 ECj/ Liter, bur in. the firllt esse [H+] rises by 2. 2: x .~.o-12 ECj/l..u[ct",. wh ik in. the second .it rises b)' O'Jl:lHq!Uter, 3.lmotilT: .5 x Ht times gtt3i1:er. Desp.itc: tM~ elJJi.ot.mOl];,~di~ f.ejjen.ce~fi~he [H'"]chajjges,. the pH cha:[ige is the same in. the t'(ij,110 clises"nJifi'i.ely, 0,31

41.9 GiA!M!BLEGRAMS

A conve.I:I:iJei:l:~~e.rmii:lo]ogy of~en used d]nicd~}T refers eoehe [SIDI nee as a ''"clifference'' btu' as, a '''gap/' Often t&i~r.e h ~n ~hlpliG!1L~bl1 of a gap .in Qu~kl:low~r;d~ of i[:&i~ ~dem;ky of at l~sst some of the kms involved .i:nlI . .hl3'king up th is "gap,." aswe shall sccjnthenesr chapter. \l'e

fi1a~! think of the phy::;i('"a~ fact that a pOiSudwe [[SIiD~ va]lJt represents Jifi dec~lfkJilufi1lbala~n{ie or charge "~p" d~a~, must be fiJ]]ed by excess IOfI"~ ions ina solution such as our CO~-free [Sf', becrlliu5e OH- is th~ (Hl~y 11t;;gat~ve~.y ch~:rg:ed.we;ll: dr;ctwlyte ion l:l[oe.s~t1:t In. s~.c~ding cllapters we shall seethat w.&ien other weak de:ct:w1ytcs ere p[QelJlt, how this St:ifnlJJig: km"gap"~sflllcd becomes more complicated,

A clevee wsy K) visual izethis _g!1LP,. ~5 well as ro k,er;p t!l'aci;:: .of the lank OOhlll'05utUon of ~. 80~1,l!· tifJ:nlI,Wl'I!~ introdaeed in 1939br a pc:dia[tUci>1:n, Dr Jl. Gamlb~e. His diagrams are :tlinw universal- 11' caned "gafilllb]egutm." Figl1re 4+.,5 i3ajj. e:-l\3:mple arnd. shov;rs the gaJI!'ib~.eg[afi'ilffi"Ot the CO2-free [SF oOf'I:'ll.b]eU.

1[66]

A g;ambaegram oof:ls~s!}s of a pair of¥el!'~ical bars, one fol!' caJ\:ions,,~he oeher [il.r anions. 'The heigilits of the bars are l:1l:'OlXlfdon)l1 00 the total oo[Jjcet1t~dol]s of the l:tOsitivt; and [Jjt;g~tivt; km5~, 'so they 111U'S~ be eqeal (dr.;crtrJca.l t1e~t[1lli!ty), A p"Q'por~l.ol:J.a~. 5ect~Q:t1 Qf each b.al:~5 ~lloc;IJted 00 each. individual ion slJccks.

A gan~b~egrIlIIl makes dear tb~[ ~hel1; ~:re no "s;a!Jts" In ionie 801~don8. To asll:u,;'Ihe~hr;r a psrticnlar N 11+ Ismatehed ttl '.ll particl[]br CI- or DB- is hl~lI:nli~ngl~ss,lb.ecause thd:1f lI:lftan:bfl:tl(])~nt inli. dl~: diggrnln is corulp~~rt:dy lItihurrI':ll:ry. There :simply is no N a(Jin '.ll gllmH.cgrnin.

Gain'blegrIl11l$ are alulays he~pfu.lin understanding the ;;u;::Ud-b.~$r.;be havioif .of S.ollI,l!tiQt15, ;md th~:[:~lIdet iSl[]tgc:d 10 draw tbem frcqll]cmly. An~t:ill litde practice, yuu w.m~ fccl. able to do them ~.IUi.}mur~e1lJd. Do Notl It isremarkably easy to fo~;:et impor~1lJ:IUi~Gompo:nenb or notrealize th a t rou have lefe sDnrerh]ng om. Drawing dlie (hag~mcarefuH}' isexceflent inseranee ag,lilnst this and will t:horougMr !!e~)ll}T~he m:1illill~itu.e llind effort: i~ requires,

The solution secreted by the gastrk ~ll!U1.CIQSa wasmentioned in Ch~J~ef' '1 as~~L[lg 'V1;1}, add, lIS high '.lls.oj N "HCl,.'''which .in~lI[15 [ft·] ;:::;LiOx '.~.O-l Eq!Uteit, pHLO. Thisre[[(])lIirk:abk fluid is manufactured by~he If..:ymic cells from the tissue fIujd:m;r.fml:[i!dJllg~hefiil.; which ~.D. mlrt'll.ls derived fromthe plasma c:iffulM]ng~hmugh ]l. The analI'ys~s in dl]S dia~.Jl'er permits us m under.s~a[Jjd I;he' ne~I;e8mk vl;~y d,,~:r~'and 'simply; These ceUs tllkr.;~h"k tissue :flmid, wldl a normal [SID] valae in. the ndghbo.rhood of GAB EqV:I"jrr~:[,. lIrtd change irr~o 11. solutnonin rrhe :st:o.mmch with a [SID] value of OJ E~l!L1tet. The Gn.ly stronglou p[!e::;em: in the gastric secitetio.nins~gniticant oollcentn~ion is 0-, so what thesecells accomplish istransport of CJ, but not Na' or ~.ny other 8t"Ong ~o[Jj. from ISF tothe 'secr.e~ed[l~H. rrSPi5 co[lst~.tn~r [~newe.d b~r the circularinlig plaShl'.ll, so in effect the G- h:as been transported :flfUin plasmatc stomachlumen. The eellnl .. ,[ and molecular meeh .. :IUi:usmiI;s !by whuch this resnk is achieved 9!:fe not}"'tt understood, Some weak ions mnstaccomp .. :ny the Cl', but these can. be Of[" moving in the opposise direction, H'" luov.ing inrhe same direction, HC03- mmr]ng inthe opposit:e directioe or anr ceralxnarion, Theeeis no way to distingll;lish eKpe.rim"ntal~y~etween H+ and OH- movemeats, b~tin(li[-e impouant, .it dD~5. not rul;l[ttcr.Wh'.llt matters L"i1hllt no :st:mn:gclIil:ionslix. allowedto lIcco[[(]![l!any th~:

Cl', Th~;sus prob .. b~'y the only sohnien in ehebodytbaecsn be understood so s~.mply:, For all the others, we mU!S~ abo tale irnoaccount clianges. in carbo]). dioxide or oeherweak acids, a weU as stmng ~OI]S.

Tile essential role of [SIDI in determining [H"] d!e\1dopedin~hi5chapte.f. thus simplifies v:er}' much t:he ~JroUernJ of a:tuJyzing ehe mechanism o.f seomachacid seererion, CJe.ar]y,~he g~,SdQ110S nOt how Ls H+ 'secrl;~r;d> no!!:' how l111,1dl H+ is 'sr;cre't~d. rr;t is not ~e[Jj.po~s~b]e w ~d~ whether H"' is secreted; c:Nchllrtging OH- for CI.-us indj:lldnligui;"lh'.llb.I~ from ti.Ccttdngboth C1- and H ", The effect in dtherC1lJ1:le isatraosfer of CI.-~h1lJt:ilhets [SIT D:1and!~t is [S~]DI that determmes [H+]. as we have seen, 'The cpestion is very simphY. how do the oxyntic cd]s secrete Cl-? Secreting H+, byitse~f> ca[JjnCltrl;S'L,ll~in an ~dd so:~tion;. no dl)ll]ge ~n [S[D]I means no ch~ngr; In [T-P].

The other half of t]]e~uesti:on ]s.Wihat happens to d:lie ]SF frorn which the 0- h<1ls been re- 1110"le,di? Tics [SID] shoukJlrise,an,diit shQ~ld beeome mO:tl;sJk~~ine. ]:~ ,dioes,. bu~ only slightly, fQr tile l')hy5iol.ogkal.f~!ll5Qr.I. that it iSCol1stantly p..;lt'fus..;d by~he d[~~~~dr.lgblood plasma, 'so dla~ its I[NOI!.~~ and [C~.-] and {hetcfDte I[SID] and [Jl~] ate nr:JiOl!~nt\]~nea. C]Oi5.C tonnrmal, No.r.rJdhde>s" the plssmaleseing the stomach has had some of i~s GII- remo\led. bj! the a.c~iv~rr ofthe O:K~"ITtUc cells. so rfu:a~~ its I[SI[)~ is :digll:uyabove normal, The ehange is observable and. has been referred to classically as "the !l:n~al inetide,"

Onen:tedn.g the: duode:rmfil., theaddseiLredoii. from~hestl}.m1lJchus. '~netlJt[a~~>!iea" by p:an.creatic juice. This secrerion is :tle~atiye1y .~ow in a-" 80thM irs [5]D]1 is high, and ]t should {hellefon: be wry alkaliue, ]:~ would! be ~r CO2 were not l'lir1;,sent, ~5 .,..~ ,shall see In CI1aprers 6 !lnd

7. BCC'.1I.usc of~tt high I[SID] '!,"3]iIlIC;, when panercatic jll[]kc mhcsw.ith the g:a;~tfk aeid a sohuion results witbnor.m1lJ1 [5~]D] 8t[iid therefore normal [H"], In ro[IJvent~.oJ'IIa,1 te:rln:unologr,~he 0- !:ili the g~:5tric juice n.eIlJtrn]izesthe NaT ]]'1 p:am::reatic juice.

1. Strong ions, dedvl;dfu.l\nr:I ,stro()ngelectro()lyt-..;s, a:resJways (:Oillpletdy discroda,ocdun. biolQgua cal ; s d"Ludoml. T1~er do not particjpatein cheneicalreactioes iDli. those solu[:&:m; s, l~heIrCJo!l.l:. OI!.~~ that matters is their ch1lJrge. Their effect on [H~]aiid [OH-~ in solution isentirely depeadene on the ]].et~ SHoog ion positive charge, ca]lJed here the strong ion dHf'erence, [8]D]I.

2. In so:bions CO:[ItgiDliing only s.t[jong ions pk~.s H+ and OH-, [H~]I and [OH-] atco()ilnp.lc:tdy aete[fi'i.~.ned !by~he v:alii)e o.f I[SID~ and theW'8!tef ion p:roa:a.ct, K.' w !by Eq~~1lJdDnS (4.3.4)a~nd (4 .. 35). To <11 ye~r good. <1I~}prm;ima~iaf:t, when [5[D]1 is neg<1l{.i.¥e (~,cess sn'al:~ acid),. [H'+] .=::::= -,[SID]] ~nd I[OH-] ;;;; K' ,,/][8ID]. Under these (bk}~og:kally very~n~8usJ)oondli~rons,. !ldding H+ as part of a s[wn:g acidresuks in >I:Dli. iDliclrC,'.1I;.~e of [SUD] [ustcqual to the amount ofH" added, [1:'11 most hOCl.~.ogkaJ sob .. uions, [5[D]1 is posidve;, a:rrla. under thesecondltlD[lS [SrD] .IS veq! s:maJla:rrla. dl1lJ:nges onl'y V'eliT s]ight1'y with .cha:[lJges iii [S[D]I.

3. The pH versus [:5]D] or I:iuatkm CiIlI:fVC; is " H]([If"Lt.~ing :.mdmislc:adirtgttcp:tcsc;Dlit'iltinn of how [Fl~~ changes w.ith [SID].

4, Because (.f:-]f]] in stmng ion 50h;i1t1Qr.lS L$ dere~fll~r.led only by [SID] and K' w' (H-f]]c!lr.l on~y be chliDlig:cd in 1>1J:ch solutioas by dlllng~ng [S~]D11.if K'w ls GOn~~[3Dlit. [H+]ch:.miblc.'> cannotbe U[lae:rslooa, or e}lph~iiedj, in terms of 1lJdduiig H". Obself'CV'eidchaiige3 il:'ll.I[1-]"1 can only be ineerpreted to mean that: stroi1:1:g ioncomposition of the solurion has cli:an~d, noeehae H" ions haw been a,d,d..;d 'Oil: :retuoved.

~. Tile add-'b:asebe.ha.v:uotofCOl-f[\oei:[lJJte.fstu~i1lJ] fluid can beexplalned~!tla.ndt:;tdV'dr in eerms of ies 5]D v:aLes, because it: w.l'It:a.ims no signi ticant eoneeerraeions ofwea.1k: <1Icids or bases (T!I!IWe 4.1).

6. Ganllb~egrufi'1Sp'i\wHe 1lJ useful v.NIy to visaalize ~.o,1:'II ·con·Genu~:tlt~O:[lJs aJ:[iiathe s;ugiiHicaiice of electriealneutteliey,

1[70]

[1Pl'iRT ]- lH!ow TO IljIINID'BII:STAMU ACID-BAsE, STEWAR.r'S, CLilSSJ.C lIE:U]

7.. The fOJ1'ma~ion of stotl'lach acid requires net mOVenlenr~ of the sU'Otl:g ion. Cl from Mood r~aSjll:a to ston<:l~ch hilmr.;n 00 as to p1coduce ~ .• ~~.~ if)~ga~ive [51 Dllvalu~un th~l~ltm~n, SQ'ine weak ion 1111,1St: ~llO Il'l!QV'r.;':,. but B+ '$~c.retio(] or iJ;1::!il.n$ro~t i.$ r.lotr~II,l!:~~d :and byu~5df QQuid not 1lddUy l[hc~l[]:miiIJ.d HI[]~d.

[CHAp:TER 5]

We',ak Ele'ctr,olyt:e's and Buffers

Weak: dl;:ctm;:dyte,saffe-ct dl:eadd)· base bellav.io!r ofaqll,l!eous 50~utions in morecompl lc;lttOO "va'~'s than, suong ions dio be[:.'I1I1,l!s.e[~l'!::~'~n[:rodilJlce gdd:utnD!n:.'l11 oqll,l!iHbda~nvolv~ng H-I- U[ OH-,. :][] body fln~ds, \'!,I\e:w]" electrolytes are U3ij]1tU}~ weak:. acid.:>, so we shaU emphas,ize~ihel:n in, this cll:wpeer, FOlnmm:dy. the a:l:lialysis dtll'~ produced 51Jch illumiinilltmg results in the previous clia~}~e!:5 ~'Q!rks equally wdlhen;. although {hr;: nCJJ~lihet11a!k~~ 'ootnple:;::j~y t$ much gr~a[er, As [lI:Ohllsed. 11105t of th:.'l1i! co.mplex k~' willbe tdl:gat:c:d to the: Appmdix of thischapter,

One result of l~e additionalequilibria in ,,\;-;eillkeiectwlYfe sO]!Il~iom isthar r]]e analysis pmduces 'leroy largr;: 'all~OUt'I~S (lifdeta~,~edun£O!l::inada1'l, Rathel: than the three graphs th~Jt 'W",1"ail~ '>ivc;[Ieroed, ttl d~sp:by tlle tDt:.'I!:~rn:ng:c ~_lf acidl-base beha'lli~y.tt" i:1JI. :.'11, su,ong decuOlytc s.ulll,l!ltiu[I ,i:[I, the: previous chaptet;wm:ny doeens .of such gruph.::; would. be needed hereto tcl]~h,e complete S~01ty. We are therefore forced to select only those aspects of weak eJjec:~l'ail}'te sohrtion behavioe l~ilIt al:e I:I1QS~ p~1't~:(]e.1'lt for: ul:ld)e11Hal:ldung biological ~y ih1po!ttatT~ csoiJudoncS, N mhing ~,s~0S'~ 'by~hus. however, lbe:CiLu;,;e: t:he:procedute we must use to a:ttiv:e a'[ '[his SiJf1.aU subSd is all tho;1[[ i, needed to ge[l:eulte tbe complete story also, whe:nevet that: is desired,

The aeid-base bella,do!~ ·of anywI;:~1;: electeolyre sO~lI,l!dan can br;:!,J!:r.I!derstllood. ~.n d,e~ail b~r dl:r;: procedures devdoped inthis d1."ilpt:c:;r.Wc, therefore begin by g:[I111yzing the behavior of 3. 5U]lI,l!z tioncontaining al sJngUe weak acid, lIA, as well a:> stmng ions. Such a solntioncsn be viewed as the result of s~tltrply adcl:iJng HA to the S~!iOll!g ilon selutions ll:illliyzed. in the previous chapeer, l~s an~~'sus will .~~~s into ~he I]~ed for: ~lQhl['JU~l;f§,as wdlas tile concep~ of bIl,l!H?drng, and wl:U providethe lb:.'l15:U5 fotq'lliIndtativc 3n3.lysis ~J,fte:.'l1~·H£i: solutions that also enaeain CO2 (Ch3pt:c::rn cianci '7).

In addition to s~ro[l:g:uom, ",V:Wte:r, I-t a:[l:d o.I-]", :ll. \'!,I\e:wkaddJ solutioa concainsthemolecular species, HA and A-. TIle strong ions are represeaeed bytheil electrical resultanr, s:peci:tiioo by d~e

value of [Slln] , as ill Chapeer ,*, \'l;rMe:l:'COllicen~:ra~ion is high, as al\V'~Y1>., and assumed oons~~nt; ~I"$ value isincluded In the Vl'I!:~UJe of [(; IF ('Or the solution, Wha~ we knO'wibOUJt HA and Ais t:h:u: ~hey must 5;IJddy~heuworeqUJh:etTlelJllc$ of'dis50Clad.on e:qUJUlibrlUlll and wn5erV~!lon of [;J.l';lI.:!>S fOI:"/1." These requiremenrs p~l1.;~ '(.'\I'gtU dissoc:iat:nO;['l iXJl[]i~ubtjl[]:tn atldi. electrical nelI[l:'a~it:r perrnit us, .or better, :1fel]tl:ire U;S~O write the fcl]owing four s~,n.n]]t3:[leO'ttsJy vaJidi,indepen.d!ent qUlllltitMive relationships, between the four. unknown, dependent variables, I[I-t]. [OI-rll. [A:~ ~ndl [I':-]A] anduhe~wo extel:ua.lly ClQlJlltL{)~.~e:d, ~lJId.ependent vadib~e>$,. [SID] and lAr1}T']'

(5.2.1)

"'V:Teali: ,mdd d:~ssodlltio:n: [H] [A] K.... [inA]

Weak acid eonservationr [H.A·ll [A.] [A.¥O'f]

(5.2.3)

ElectricaJl[lenltita~it~":: [S]O]I IOH] I[A] [OH]I 0

(5.2.4)

Because we have font unknownsand font' equarions, \lI\e can solve for the u:nk[low[ls ~! the s~me sy'S~emll,tie eubstieutingprecedure we used in Chll:pters 3 and 4, The resule, preseneed ]itl the Appendix, L$ " set ()f f'Qul!: ,clJbk eCJlJlMions, O~S$~~Uy, whidl in dlls ~$$~ means '''befof"ie ({om~)l:I:tc[S,.'· the quantitative analysis of acid . -basephenomenacarne to a plll:'a,l.yt_:cd. halt at rh is p·o~mt Gedu[lg values for [H"] from irs cnlhice~!na~ion, guven va]nesfott' [SID], [t\"oTI. K.tLand K' wal~hougjh possible .in p'J1']ncipJ.e.\!?1Is so long and tedious a process as to he imp.mcr.i.ca]. The whole process ofg'l,llalJldtadve alJlaly:$ls leading up to those cubi-c eqUJadolJl5 ''(ll,'';lS. the.ref'Or"ie gel'H~Lallv diacerdcd lIS useless also,

"

FomJ:f:t1l:l'ely,~he developmene efcoraperers and programraable calculators h~s oo.m~)]e(.cly changed thus 5U~lJa~Uon, ]l15 now jnst ;1:$ easy 00 ,solve such e:qUJ~iclon5 ~5 his to solve a s:illlple quadmric, The cot.nplIrret does all theworls, and the, numerical tech:!liuCj:ue.~ wHili: [usc 115 wellwith the even more COfi'il:p.lkated! frmnh- a:[ldi. higher-o;rd.er eq1tatio[ls tha~rest]]t: wheD. v"re mm. O'i.U ~t~elltio:n to solutions ]]:keblood. plasma, The general procedere ]8 presented ill the Appendis

w tht$ dlapte:r, PeQm a l~l:-acticalpOlnt ·of v~ew, the Ap~'}endlxm;ll!ybe vnew!i':d ~s the analog fOil:

I:his week add sollltno;['l of the one-Iine fnrmulafcr sfJ~'ling agllliJdrni!ic e:LJjlllltion [hll( we, used in ChaJp'tet 4+ eo go from EtpJ;:Hnon (4.2.3) 1:1.".1 (4.,2 .. 5),.

This new [a-c~,~h~tQO'llIpUJlrel:st.na].::e ~'}r:actka~ the numerical solution Qfpl:i;vUously useless e:Cjuarrno;['l So!:ts, dl:.1llJbl'Csp'wfound~y {JI[]:I:' ahi~ity to understand acid- base p.he:no[;Jlc[la i[l.liv~ng sys~ terns. It permics the tho.ocrughqnll:[ldta~j:V'e approach thatis the mtUo:nJ]e for this book and that dis~iitlgwshes. t:fuis ~lIal~1!~s from convenrional ne~J[:IIl.ents of the subject. Throughoutthe rest of this book,. we shal~aS51J11l:e that CIQt.npl,l~erl:mplet.nen~lI!.idotl Qf~hese genl;'r:al ~lm:uCJu.esus a~vays available, 00 dlllrt: ifwe can wrire tile lIppropdarreequ"llti.oIJl~~,. we can. s= mimerical answers from

[1$]

them,

The ccmpnrer-implemented nU!merica~ solutions w the foarequarions describing aweak add :plus st[-Qng ions in'J<'";II1;e.[ p.r-,esenuIl,l!S with a laf:g~atl1QII.l!t1~ of inf'Ol:dnatloll to d~g~5t, Fo!!::'tll,l!nlltdr, nne of t:he; itldic=:pe;.rtde;.fi[V>ld:alb.lcs, n.'.llindy,. t:he;: t:O[!I:~ amouut o('<vcllk lId.dp~n!,~5. USt]JUy rather well regulared jn ]l:- ... ~.r.ag sj'stems, fo.r reasons not di.i.tcctly related toacid-base !CO.ili.s.i:der:a~ion.s. \v'elIliliY du~reiore restrict om a~te:l]~]on. at: least ]:l]i~ially, tv variations inthe dependent va:rhible$r-,esuh;~[Ig on~y from ,ch',lnges:un dlr; other ~:nd!(:p'enden{ vsdible, 'Jhll~beh~l'Ilk~!E~5 presented in. Figntes 5.1,. 5.2,. and .5 .. .3. Th-er wi.llte;par aI:reflll!.l 5tudy~ including cumparbon wMl tbeircounterparts .i:ili. thepb"e:V~ous chapter, The fdlo""i:ilig poi:n~s 1100 espe>ehtl]yimpO[hmt.

l;Thecl,lfY~ f'Or [HAll ;;I!nd [A-] in F~gl.n-,e 5,la:re SUil:~'liris~ngl}' li(]~r and syinm~i!;d:t;:.al ;;I!IOOIl.l!{ the mjdpoinr of the [SIT:D]itange from aero 10 [SID] ;::;; [l\m]' (The; dJe;,gttc flfdhsodllt~on.,. [(, fOJlO"lTS a curve JUSt .Iile that for [A~ because a: is directly proportional to [A] when [~J~]I is mnShl.mJ

2. T.h!llt midpoint, at whi.ch [S.ID] ;::; [l\tHV2can be seen f,,-on1 the eqll,l!!ldfJ:[IS to he the poi:n! Jt wMch [HA]] = ][A·]] = [SID~= [A,'uTV2, 0:, = 0.5 or S{DfI/.:J, [f[+,.l = KA, [OFt]] =[(' '(l/[( A J:nd pH: == pKA, neta;iled analy1!is ofthe e~wtiotl.s showsrhae these eq~a]]ties <'Ire valid on~}' so

~fJ:n.g..'iI.CS K A b wiJth i:n.. an utde;;t ofnJlJlIgnitnd!e or so of Jk 'w ,De;,. i:n. the ndg~lhJItt'hood of :IO'? Eq/Liter,

3. Over the [SITD]tan,ge from zero m [~)'I']' [Btll L~ inm:h l1I[ge:tt', end-changes .in.orernpHlr with [S~]D]] than was the case in strongion solutionsatthese sa:me ][SID~ values, T11e [H'"] and ]tOfl~ cnrves are no longer srmnretri.(;a] ;fl,170U~ the ]]JerJ;~~nd PO]ot. [H'!] == [01-]"]] and th:a~~ ~}Qi[Jjt I:lolongr;t' occurs at [SID] :;::; O.The pr-,e.sence of the\I,"'eak ~f;H .~r;oguir-,e8 th!l!Jt some-excess sttt'ung base cat nons hi: prese.m when [H+] and [0 H-~ are eqll,l!!ll. Conventloaal [e;t1Ui:n.{];~ot1'\\1'Ouldsay~hJt sO.me StfOr.ag hase is. required to "neutralise" theu.reak Jot::klL That suggests tha~: [Ft1 == [OI-[] shonld eccur a~~ [SfD]] =::=. [ft,OT]] which Figure 5:1 shows is far from d'te truth, The 5jtuadol1~8 best under.$tood by~gnizil]g that~he [SID] valueat whkh neu-

tral kr occurS depends on the spod tic fG'lifms flfbolill the; [[-]t]llIrtd the 1[01-[-] curves" whkh Ih.TIec!l[ls i[~s 11. pmpe:tt'[y of the whole 5)·5[e;111. Any chll:n.ge; In Il.'\1'(H1, KA, K' ww.ill ch!ln.g:c ie,

4, OU'~sid!t;; the ZeIT) to [Ar[)T]r~nge focr I[SID]" [H+]land I[OH:-] beh~l'Ilr; very inll.l!ch as tht;y do ill snjong ion. 5nlll,l!t:if):IlS w.ilihol]Jt,<vc;lIk lIdd.W1c.n [SID] is ne;:gadvc, [H+] ;::;; ~I[SI[)] and

[01-[-] = -K'w![S[DI] asbefore. When [SID]] is pos~)t~ve andaliove [}~OT.1, ][OH-] = [S~]D]]

- [AY<H'_1. I[H~]I == K' wlG[SID] - I[AwH]' and the syste.m behaves ~ucst like a strong ion. only solution with the origin of the [SfD] axis displaced to [~H]. These properties are re.f:Ie'Cted in the j[[:.]f] and [OH]cuil:ves at the top of Rgll.l![~ 5J as wdl asstthe ends of Figu:rr; ;,:2..

The curves ofF~me 5J. and. 5,2 present d:l;e~ua:l'l.ti.bl:~ive rebt:ionsih[psbet.ween the four

I:nlterl:lal or dependent '\7,uiiMe,s,.I['\:l, [HA]. [OB] ;;I!.t1d I[H+] and the s~ngle .independen{ 'lad.iMe,

1[74]

[J",m!Hi-O
-[J,,[J3 -[1,.[1(1 -'0.01 0.(11) 0.01 [J,[J2
SID (l!.~l/l)
LOE;"'6
- S.OE~'
:;:::
11:1'
~~ 6.oE;,..7
!Ii:
'e
"~ 4.0E,.,"
1::
~
"'"
:1:: 2.0E;,..7
O.II]E+OI
-[1' .. [1'3 -[l' .. [li2 -[l'..IH g,I][I, g,l]l 1],1]2
5li~ {EIIll)
3:,I:H::-Z =: c "1:1

ii l.(lE-2

+ :c

0.05

ir 2.[I,E-2 -I- HA_,, ,

IiII

'r.;.,r.

11).(lI:+!D' +- __ """T....::;:A_- -"""T---~--___,_-----!"r_--"""'T'".:.:H~A"--T'"'""--..., -tL'1)3

FliglUlfe 5.1. [19I~]I, [OIH-]II[HAl o;!nd [;10"] ~r.5U:5 [S,iD]~l:Ir o;! wtii::akacid :50~IU!tul;m. [AroTl';;'OI,02 Eq/lL. and KA"'2 x :IlO-7 EQ/L. TIIl,e: ll<'w vallllJefoli" Iplasmal ls used, 4.4 x 10'14 (EQ/lL.IIt:er~2, at 3700( .. The venl'cal scal'e: ~lfii th,e: middle ,glllalPlh hes beelii expanded In OIi',dler Ilo slhoVi' how I[OIH-] aln:dl [1HJt"ll Ibe~alve 'over ~he I[SID]"'O~o [5IlD]I"'~o'T r.ange:. rne hOIrII:oo'ntallscales for [SlID] are the same, almd ~lm lreglstelr, mil all th ree gila p,l1s.

[CHIIPTER, 5 - WEAK ELECiIlROLTIE& MW [Bl!FFEIf!;&~

[7,5J

1JJE,.2

LDE-~,

strung Ill!n Differen_ {SID, Eq/l}

tiiAr s, IH+'~

O,H- {"til}

:~"IDE-6

U1E,..j

:LIlE+D

strung Ion Differel1l_ {SID, Eq/l}

[FlIguli\e, 5,,2. L.o~Hog plots or- I[Hol'], [OH'], [lHlA]and [1\'] v-ersus [SED] t-or~he S<l,li'I'1e solluitlo:tl as ~I'I [Fligl~l1'e ,5.,1.

[SlD_] , when~he othes ,i:lllIciepe:nde.lllIt variable, [~y;ll is constant, and the system. Is in eqtd]lbtlUlII. 5-:a:~is[;r]ng Bquarions (S.,2J) duough (5.2.4~. We shouk1. also like l'Olmd.e:rManci qu;a~i:~atjJ",e1y ';],,'il)a~ piEooo$ses~r;~d to these equil~~duj]l results. and hm"uheyul1o;li;Ic~.

Suppose thaJt in the SO]UJtiDIllI describedby these t'iX'Q ligures. we lbegin 'i),!,iJth aJ [S.ID~ Vil]llle of + 0 . .01 Eq/Lieer andthen ra]se [S[])_] by addling 0.001 Eq/Luer of KDH. The immed]a~~ result j~$~O' ~:I]cr~s~ dl~ ~N::~S5, 5tf'Qt1gtol1 p'ooidw(;hlll,f'g~ by O;(:I(Jil :18-q!l.irer 50 th~J!; d1J~ I)e~ at.nQun~ of ,<vc;lIk electrolytes ions lbcadn:gn.c:ggti'!,'c chll:rgc mns .. rr :.1l~t;o increase by (IJ,Ont Eq/l.kcr.1<hl: onlillr ~aJk anions avaihb1e ate Ofl and A- andwe have Jd.ded. 0.0011 Eq/Liter of OB- aJlbngwi~h the K+ so why does anything have L'O hll:ppe:a? Wh}T does [O[::lJ not: ~US(: go u[) by o.mn Eq!Li~er and ~v~eything~~se ,~tay J!;h~ 5am~!ll.8 k W)ils'? \Vh!ll~ "actu~lly h~[lPeJ1S, asuhe C~.1fV~S sho'l.v. ~~~~h~.t [OH] ~,1:.1l[d:llychangc5 at :.1lU! h increases !by.bs than 1O-t: Eq/Utc[, and [H'] goes d!()\iv:n !by:an. even Sfita]]e:rMiL'U.ollnt'l!{7h<iJtgoes up by almo6~ e]{act.ly 0.001 Eq/Lirer is IlA-I.,

The r~!ll.SOI1J. for thes~change8is thatthe added OH-,a.hhough i~ could in prim;iple serve ro balance the added excesspositive c:hll:rgl:: onthe [(f also hgs~he efk.c:~ of d:tliving dll:: waterfotfii.ing tealt:tion in the cii,jjectioilli of more wntf::lfand lowered [H"]. The efft:c~ of the lowered [Hl ineurn, is L'O d:tt'.i:ve the HA dissocianon reaction in the direction ofi:l1i~re.ased dissociadO:l1i. thereb~? formul1Jgmo:Jit.; A-, TI1e over1l1 ~Jfect of the rwo pmces5e$Ul1~1tlCdl1g, dlr;f'dore,.

1(76)

2,0 l-------~

:1.(1,0-

i 6,0'-

[),O _----".---------,,---------.--------r-------r-------,

-0-0-3

is to [!eplalce 0[-]- by A" The aclldlecl. OHus iLou.u.,'etted .i:lili,to 'i.It.lli!e:r, btu more HA dlssocistes, so t1at: proper [H'] and charge balance are .re-stmed. Now the question becomes, why do [H'] and [OH:-]chal:Jge: at ;1I:~I?Whr does A- nQi!; :tt;~l~;1Ii;e Ol':lcompil,e~~~y and leave [H+~ aod [on'] JUSi!;

<IS th.cywcttL? The <lrt5wc:;[ l ies p<lnlyin li:11:e relative magnitudes of thcwerer <Ind. the we<lk add d.bsoclad.o.Iili.G01n5rtantsand pallfd"r in the fact t:halt this 1:> a system, 00 that all four ofthe playsical requirementson ]~ mruc ru~":5be ,sa(~sJiJed,i:lo~ ~IUS.~ eleetrical nemmity. A- ]a:rgely replaces OH- because KA is so maeh ]a~:r t:han K' w (wa~er is a veryweak elect:!::oO.~)T(e), but i~ cannoe

do :$0 wmp~,e~dy because when alluhe r-eacdo[l5 have settled down to eqlilJuHbrJ.L,llll again, [H+] [Oli:-] and [A] not on~y h.IJVCiFO sgtL~fyEqu .. dO:nli (5.2.4)fi.lt ckc[tkmlnlimtm~kr.li:hcy also have to sadsfr the other tbreeequatioes. The end :rest]]t is tha~ [Ofl~is ;ill. Htde hughelJ:' t:h:ll:rrI .. itwas, [H.'I-] isa ]i~de lower, [1\] is rumo6~ OJJO] Eq/Litle:l:' higher, and [J-:[A~ isalmose {l.om Eq/Liter ~o~:r.Whhjn the ze~Q iI;Q [~')I!",] l1J!.t1ge of [SIn] there is no si:n(JJp~el:""~y to ul:J,d,t;[:5lal:J,dj "",&i;1l!t b, ~.1.appcnJnlig,. The hy point is t:h<lt tbie:: watcrrcaetinns are [ust :IS impo:i1um as tbie:: weak add ones, Neither one alone can explain what happens.

Ou~sj,djt; the Zt;m to I[A"tIT]r:aoge", theee a[e~wo ~~1 duf[i;[ent~~Qns. ~us~ ;115 there Weft; bJ:ffJrCWC: added weak acid, When [SI D] bnlie:g<ltive,. it mustbe lb<ll<l:ri:cecl.b)' positivdy clli:lrhrod weak dec~ro]peion:s;, :lllilicl. I-r is the o.nlly one s%~.~.alb:le, so [[~r]=-[S[ D11.When [5]DI isposirlve and largerthan [~)T] ]t: .IUUM bebalanced by llegativdy charged weak electrolyee ions. A- and 0.1-:[- are both avalbWe,. but [11..-] C;1I.t111Qt exceed [A,.m] so OH- has iI;Q till the gap still n;lllalB.lng,

[77]

'Tha~~ is why [0 H] ~ ([SIDII - [1\0,-]1) inthisregion,

As .Iung as [SID]us,<vcJI. within the interestingrange from [SID] ;:::; 0 tD [5]D]1 ;:::; [ArLIT] in 11 singJe weak acid sokition such as this ruJi.d K A is within an order of magnieade of JK .~ ,the ralQw.ing: forl.l.lu~.a$ .lnar he e:asUy deri.wd from E~Iu.atk)l]~~ (5.,.1)~hmugh (SA) !J!iI:lda~ 'QJten~&er~h

[A.] ICSIID]I

[H ] IK .... §[Arod tJ
§[S,]D:~ 1~ [OH] K 'wl[[~]

Exu::pt: forthe ]as! one, these: [b:tnJlmlas lItt: only 'I,'>I.~ id in 11. 5ingk \.VCik: ... dd. sn~il]jtio:[I. and only usefsl :uf K A' I[~)TI lnd. [S[]J]arekrJ(fwl'I: tlleyn.1a}~ he te:aitTIl!:nged as desired if ()~he[ pl:irs of vlrbble:> tha:nll.l[t\url and [S[D]I have been measured, bt]t only if [5]DI is known to be ""it:hin the range specified can tfuer give ~lSll.ble numbers,

Moot b~.0I~.ncJl sohnions.andall body fluids except Jdd gaM:d.c juice, have la[ge pos~dve [SfD] values, well above [!\-orJ1 for anr \,~ak acidpresenr, bll.M~ theiracid-base behavior is verT d~ff~f.l;tll from that of Figur~~ ;,1, 5,2, and 5.3~ec.jluc~e they !J!.h,O OO£lIl;ain carbon dUO'Kid~, We sh!J!.H see in. the next two ch~ptel:s wily that [Hakes somUich dLff'e'r-e[lce. Fr-om the ·analysL~ so f!J!:~> the [jfUC.~sllbn::: isthat whc.n·evC[ CO2 .it.: not pr.crseH[ and the total. lInlOIJ]:[It of weak acid h~Cl(J;[],~t:il:nlt, then what determinesthe [H"] (or pH) is th.eItf::S~]]w:nt ofthe stOOnllg ion coacentratione, expressed as d:te [S.IDI and. how ]( compares wit:h IlAmrj.

5.4 BU';;II:nt PLASMA,W1T!HO'Uf CO2

CO2 1.$ jlm!J!jor de~r;rlninant of the I[H+] in blood p~lI!sm!J! in v~vo,as we .$hall see in Chapt"r 7,. but :.1I:n. L .. obted. phs!lCIlI Slll11P~.e w~[l1oil]jt its CO2 can still provide. ,,:[I.itllteresdng example ofa \ij,1leJk m::i.d! solution such as~hJ~a[)a~yzetI in the p[Je- ... ioes section, Thecomposition of sucha pbS11':La. san1:pJe is Iisted in Ti1IlbJJe S..1and may be compared with the COli:l1iteI.s~]~]a] fluid .saulple de,~(;dbe-dun 'Jib~e 4.·~ of the P[-ev~ous ch!J!~'}te[. The [l\ar]' KA,. and K' w values ~n T~lble 5.1 havebeen used in the C'.llI.cubtkl11s that produced Figures 5.1, 5.2, :and! 53, So that TlIH,e, 5J

1[78] [Pl'oIH ]_. lHiow TO IUJINI~BII:STArW Acm-EksE, STEWART'S, CLASSJ.C liEn]

"iHel Added (Eiql) [C~·] [SIID]1 [iH']1 [OH'] pH
none 'O'.i1!Oi7' '0'.042 2.0 :x 1.0-~~ '0'.022 11.7
e.ei 0,117 0,032 3" x 10-'12 0,012 11.4
o.oiJ (ki2:9 (k02:0 6.6 x ]O·w 6.6 X lO·1!: '9.i8
0.01 'O'.il39. '0'.01'0' 2.WxlO-~ 2. •. 2 x il!U-r 6.70
n.ei 0..t49 0..000. 6.3xLQ-s 7JJ x :m-'JAl 4.20.
0.01 0.15:9 "0.01 on.01D 4.4 x 10.12 2.00
0,01 'O'.il59' -0.'012 '0'.020 2. •. 2 x il!U'];i; 1.70 la~lle S.l", liitration of aO~~free IMooo p,lasmal. AIIII tClllitelilillrations iltli IEq!L. Ilil,iilJial cOifIilpruition~ l[rf.I;:II·], 0,]43, [K"], 0.004; [rMg~~D, 0,002; [C;:ll~·], 0,'0'0]; [el-], 'O'.il!O'7; [SO~~-], 'O'.OOl,. [8m], '0'.0<1+2; I[OH-]I o .. .on,. I[t-ii+] 2,'0' x il!O'-12, [kym)' 0".02'0'; I[A-], 0 . .02'0', I[HA], 2!0 x 1'0'-7; .. = WO%, Palrameter valil,lIes: 3,7 "C; K' w= 4.4 x il!O"u~ (Eq/1L)2; KA = 2.0 x 1'0'-' Eq!lL.

fIla)' be viewe.d $S jl set of selected Po.unus ftD!m~hosehgu~s, By a[l~~og}'wuuh Table 4.1,u~ nCJJ~y :11150 bc:re:1ldi. :11& Ibt:irtg the,[c.."I[]~ts of dttaEirtg 1 Liter of thc:: plaSrul;,l 8aru1p~c:: with Hel." The huj,o![ cl.iflierencelbet\v,een~he resuhs in the tWO tables ls that [H~] for corresponding (pos~.dve) I[SID] values is latglt:tt' ii'll T~lble S.l~han ]]'1 'fable 4J ..

Thefirst :tow ofTabk 5J, labeled "[I0flC:,," shows thatthe G:tilgilI3~ I[,SID] value in pb5:nCJJm.is + OJJ42 Et1J/Litet.we~.~ 8ibcr"e [~YTI" We therefore have [0[::]-]= I[SID] - 1[1\ur~ = 0.0:22 EgjlUre.iI' and 1[1-]."]1 ~. K''!llj ! OJJ22 ~ 2JI x W'I~ E~!Lr~er,pH It7.ltOR~ ! [11"]1 is above lOHl, so jhis is an e:;::t:r~mdy ~U::~h]~ 5QI~];k,ll[l, The w?!lik!ll;dd is df~!;iwly ~'Otnl~~~!:dr d~5&O~u~tOO ,,~ this [SID] value; [A] ;;::; OA)2" [HAJI ;;::; .2,0 x 1.0-' Eqll.JEC:J[,

.l1t]ding O.OU Eq ofHO reduces ~SrD] to + 0.03,2 Bq/Lirer, .row 2. butthis is still much laLger than [.A"'nr] so [OH'] f!li.ns by (l,('n Eq/Liter., [H+] rises b~rL7 x.IO-I~ E.g/Li~er,\Vhi~e I[k] :1Ind I[HA] do not ch:1lrtgc: sig[Jiifk:1lrtt:~r;

At]ding O.OU2 Eq ofHCJ hr]ngs useo t:E:'ie I[SID] ~ [ATl:1T]poi:lJit'. 'The changes in [HAjl and. [A-] are &~ill ~ns~g:[I:~Eu~a[li[:, and th~ ~h~t1ge i[l I[H+] ~~S 8dnn;~niSO;;l,ll~, 6,6 x.W·i.{I EqJ/Ure~, [OH-] F.'ilIJb lbr :l~.ightly kS5 than Q,(]:U to (i.6N; W~EqlLitC.iL

The nextaddition ofOUJ] Eq of HG] pm:s [SID] [ust at: the midpoint of the zero to [~)T]l tt;gkm, at [8]D] ;:::; nor E.g/Lht;r:> Now [[A] ~ [[r-]A~ ;:::; [8]D] ;::;; [~Yr] / 2 ;:::; 00.01 EglTJter, [H+] ;;::;[( A ;;::; 2.0% .1.0-7 Eq!lJ[c:[" [0[-]-] ;;::; K' 'ill ! K A ;;::; 22. x m-7 Eq/U,rer.~ and pH ;:;; pK A ;;::; 06 .. M.FOlt

t]]]S sYSt:e.m"bec<lIuse K, ]S very dose ('0 Jk "...,. • th]s poilu is very dose 1'0 dheacidi-·base neueral ~}!)~nt, at which [[H+] ;;;: [OT-f] ;;;; 2,1 x~I)-~ E..qllite.r, pH 6,68,

One more fIC]add.itio]]. puts I[SIn~ a~ zero, This is \Vel] onthe acid. sidle of nellJll~rali~y, (Due to [he weakacid, [[11+] ~$ no.w I:Hl,lchlarger than [OH] ~~thoughboth aee stUn ver.~r small, [HA] h; vcty do".!: to 11.Atflt] glt OJJI.99 Eq/I.Jrer, g[Jid [A]~s. the SgtlCJJC: as [H+] at 6.3 x 'm-~ Eq/TJtc:t,

F~n:fuer additions afHCJ make [S]DII more and mare negative, so I[H'] ancl. [OH"]jbehave [ustas ~hey dJd in 'liMe 4J. [H+JU8 ~msl-[S[DII,. [HA] is eqqJ!allO [1\orJaJltl108!:, while [OH'] and [A·J af~ el{tl~111iely small,

.A. more precise analysis of this solution would shaw that: there are in f~ct: man}'\!Cea.k ~c:iid:5., not ~~1I;S:;~ Qne,r.;!lch at a bw c.o:[IIi;~r.I!~:[catjOIJl., All. dl~ K }S!lnd osmaU 1[~L')'J.rscQ·u~db~ .induded,un a . more precise set of'calculations, bur the netresult, 'ilHet" an enormous amount ofcomputer '<VOI.rk and timc, wOIJ]~d not be 8ugniAcamly duffctcm rm.m dle:se representative results us:ung s:~ngle K A JJndl. [A'nrr]'

5.5 BUFFIER,S,. Bl!IFFE.RIING ANa IIOUFFEIR: STRIENGililiilS

'''Tn buff" ]:5 defined in the djjc~iOi:lal'Y ~:5 <"~o lessen the shock oi,"anda "buffer' is '~~hm. ~~)khb~ff5/' In aGud~h~$r.;d~~miSlry, jl",~ak ~J;;.ud sudlgs dl~ HA W~ h!lv~ br;~n jll]"lrz~ng .in

th is dlillplCe:t~5 oftenreferredtc 11:5 g huffctt', 'lrhee:sse:n.d'illU}' uti iversal reliance uti. pH \,1111.11::5, instead of [[::I"'~ hJJS verT much coefnsedthe qlla:[ltit:ative aspects ofbuffe:l:jngin weak acid so]utiof:lls and. has ledeo ~ .. lni:5pJacet]enlpE:las.is on their supposed ab]]]~y 1'0 "resist" cll~l:l'llg:eS in [H"]. Th~g~jlndtliJ:~Uve analy.sis Sr;I:WS to dgruf)r th is situ~.tiQn very fllll;iLGh jlnd s~g~s~s SQm.~ ~m~'JoOt:t'ilntttti[:[.~cd,{}tl:5 otl. howW\:: 5hlmH thi:tlk lIbc]lJ]t: '~bu.ffe;tt'.ing.'·

In selutions of Mro.ng ]OOS oilly. considered inthe previous chapter, [H"] is determined auIy by the nlqJ!r; of [8.'l:DII in such ~. w~y th!l~ whr;n~er [S[DII is po.s~idw. [F-J+] is wry C$maU. and chllnge:s in [B+] are II minute rrn.G~lon of the changes in [SID] thllltbtunJig them about, (~e:eFig~ ures 4.1, 4.2,an.d 4 .. 3.) ~]n JJ !>olu:io.n containing JJ weak ltddl. in. addntnQl.n~o st[!t)lng ions, the\la~ue of 1[[-]"1 is cliel:ennill.ed. by~wov}u:]aib]es, [S]D]I ~nd IlA'n:lT~ IlS we have jruSl: seen. ]f\!Cecoo~inueto C:l.m5~delt' only o$IW;'.IJdons in"'~lkh I[Arr:r'l'1 dbe>$ nm chang.e. then ch!lnges .in the vallue of [H+] cae nn~r resuh f:J:j(Jil11 changes in [5]D]1 in. these weak add uillJ]ltiotls lI~so.Figutts .5.1 and 5.2 show cllea:dy~[1JJt 1[1-]"]1 dnnges in respo.[lJse to I[SIDI d1ia,[lJgts are still VtJfl' s ma I], solong as [SIDI is pOII;itive,.but thatoi ... erthe [SIDlltlt[lgt from zero to [~"nl, [FIlis much htrger ll:[ldl dlaJnges, much more for a given [S]D]I (;h~nge ehan ]t do-es aver the same [SID] rn:l1igt when noweak addis Ilf~8~n~. DU[1;C~Qmll1j~lt'i50n Qf~hr;~og--Iog [H .. ] Wlt'SU8 [SID] curveswhh and withou~ We:lI],;. lIddUti Figu:tt: 5.4 dC'ilrJy demonstrates th is flld. Ourquanrirative '.lnll.lysb, .i:tI. other words, shows that~he prese:[lJce of a ·W't:a:k JJoL:Dd. "buffe:h"':;tcm1i]1'y c~mses [I-rllw cha:[lJge fi'iloter:apid~y with chaeges in [S]DI~h:an when no we:ll,k acid is p:resenr,

In ii:e~t.m5 O'f pH, the same conelusion canbereached lbr coru.lpadng the pH, ~J(tt' t:it['iJ.~ion curves ofFigm:e 5,.5. A~ every [SID] value between zem snd [f\'OT]~h.e pHcI:I.[ve witbout weal-!; acid .. isl]atter than \vheiJl. weak acid is present.

NO[lethelless., the :presence of the weak add does mskean impOftJJ:[lt: difference. Itchanges the [H"] at pH value of th.e so]tJJdon:t~ an.y [SID] value toamore JJoL:id.col.nd:ido.n. It d:iillS a]tt:l."s the [H"] ocr. pH .mnge rharthe solution experiences m. response W a given nlinge of [SIT Dllvalues, so long ~5 [SID]I ~,s pO;$~thre, If, ;1;$ us CU;SWIn~ry. WeC(l11cr;:nt[';'.IJte on. thr; [SI[)] range in the ndghlbothood of the: I[SID] ;::;; [~.oTII 2. poinll:,wc ean go further atld s.'il}' drat the effect of the

LDE-Il

LOI§-S

LIlE-1D

HI+ (EQII)

1.0G-~ MJli-6

f,]gIUIf\E: 5:.4., Log-log pilots of [HI"1 versus [5[0]1 fOli'two sollultilotlls, one with flO weakaot:ld, tiMe otlher the same: 111S illtll IFligulIi'HS 5.1. <llndl 5,,2.

\'i!,It:ak add is to pt]t I[Fr] in tbeneighborhood ofKJ\. • .or pH in. the nd~lborll:ood ofpKI'I.' W.D~houttheweak acid. [H"] in ehis neighborhood is simply K' 'If, ! [SIDJ. a '!,'ery Sfl'lIa]] value: pH is d1JI?~ fQ!~I#r;~, on the Qr-d!I?l: of 11 ~)I~ .~ .2:_~\711J~t dl~'\:!,~~k :lI!c;;id "b~ff~~' dk~~> dl is ~n~lrsis reUs 1Jl..'>, .is ehangethe puint around which [H+] chg:[Igl:~, for g gl.'!,"c[I rangoe of [SID] values, It: docs no~ decrease the amount of [H~] change.jn fllc~ .ut increases it. A v,Te:ak acid "buffet" ~s therefore not an [H1 or':pH "regulator' but rather an I[r~n or pH "setter," ITt: "resists' [H"']I or pH cl~angtes much Iess eff"?c~ivelr tilan till? S~111~ SQI.u~uon wuthout ~nr weak a,dd-

Quandtaluvdy, the abHity ora sol~do[ll to "resist" changes i.[II [H'] or pH .un respollse to lSID~ changes ]:5 indicated by the slope of the [H'jor pH, versus [S]Dlcurve,.l'he steeper

the curve, the g[~tel: the [H-+]I o~ ~jr-] ch~ng~ in resporrse to ~ [S[])] change, aif)d~h~15do.·~

th..: "w.eaket"[hc !buffeting action, The :tt'l:dpmm~ of th is slope serves J~ g measure of buffer ''su:etigl:h,''beca~ue the H1I!uer~he curve, the larger .ut will ibe. We therefore deb.[IIe tbe[o~lowi.[IIg "buffer strengths";

[H'] buffer s[:tc:ngth =the reciprocal o[[he slope of thl: [r-]4] VI::t:;;u5 [SID] curve for g 5.o:~I[]~ non,

pH buffer S~l""if)gth =sbe [«~p:[lQc~1 of the .slope of lh~pH versus [SID] curve f'Or ~. SQ.~li,l!tuon_ [[-]"'11 buffer sHen,gth is a dimensionless number because it r:epite:Sent3 the number of equiva-

zo ~ __ ---- ..... --

~l~ ~ell:; aQid! [Anrr) ",(I, ~,

Witih wsalk ~tid [~17(>T 1'" [I ,~2 E,;v! ~oA"':2;o:l~·7 E,;v!

(I,'iJ' +------.------,-----------r;---------,--------,,--------,

-e.es

·O.®2

-e.er

le:[lts pelf Liter Of ions per Liter of s~ro[lg ions t.hat must be 9!ddJed, to or removed from 9! solutkm, in order tcchange [H"] by ] i6"1/Lit:er orion/Liter, pH buffer :s~rengrh. because ][ is the number of eq~hr!ll.il.enlC$ per Liter of [S[D]chllll:lge neededto bring ibou~ a pH dlllnge of ~~. and

I ]" sdh ,", 'U ,',' h ,,"] dl" , " ns of [('IDTI ," ,J ' , I"

P - , 15 " Jm~IJ~'l~O[l, ~58, ' , as '[1~, ,~m,e[!ls .• ons a ,p ,,~, oql[],~vlil.eDlt.'l per, .....!Ite!:: ..

.As indieaeed in the A~)pendix',~he formu]~s for d~esefwo q]u~n:~](]es, given bdow,c~n be dedvedby ,$~:r:aightfO~'m..'arJ aprHIC'adon of e1emen~~:ry ·c!ll.il-cIl,l!~II,l!s 00 thr;eg,uatiol:J$ for [H+] as III funetion of [SID] and [~Yr]l.

1. For positive I[SIJDj values in solutions of suong ions only;

[sm]~ IK"w

(5 .. 5.1)

2. For solutions cOllluinitlg awesk gdd, llA, at g mral ccaccnrration of [l\m] under the !ljQlndutio!l1~haJt I[SID]us posud",e:and veryclose eo [1~oT]I!2:

[8W] 2. IK ....

(5,5. .. 3)

pH ItnJlff@tstmingrth .... 1.2 I[SIID]I Eq llif~t

(5.5.4)

As an e:l\llmple" to indiC9Jt:e the fi1I.ag[lltUd:e of the numberainvolved as wellas tD ve:rify that adding a weak acid reduces, the buffer s~rengl:h ofa solution.considerthe CO~-flCeepla8n1;a. 50~~don of Tab.l~ 5.1. Its [~)'T']I is (W2 ECJ/Liter, 80 ·'i)I,"r.;·ne,ed to calculate under (1) aboIV-e the buffer strength values fot a S[ID:[Ig ion only s.o.h]lio:[I. with [SlD] ;::; 0,01 Eg/Utet and compare:; t]]eifi'ii.wkh the [!t311!,tS under (2) for a sohnicn whh~hesaril'ii.e [S[D]I Va~ue and. Ka= 2 . .0 " ']0.7 Eq/Liter, The results are as :follows;

No, wea k <!!cl!dl;

I[Sm]=O.Ol Eqi/Uter

Wel<!k AJ::lid; ["\o,J=0.02 I[SID]=O.Ol; K~=2.0xlO·7 Eq/lLiltelF

-,2.3)( W~

11.0.23 ISqVUltel!

-2.5 x Jl<D"

OJ}!2 Eq!lLib;lIF

Wh!l!t the~ n~111~e~,;;I,ilQng w~th the ~~·nr~$ th~l; il;hey~pf~sent:> td~~s ~on~~:ltU!ll,.lly is il;h~l; when [SID] ispositive and cgjl[]<ll['O 0,0'] IEqlHtC.if and no weak add. Lsp'l"C5enlt,[hcl] a. brg,c, number of strong ions (2..3 bmuon) must he mO\led ~.II1JtOOt our of the so]utiolnun onder ro change [lf"] bYi~n~ "1 H.". The reasoe forthis is th:lJ fOj·l~ ]8 also cl~a:l:lgjng, a~lllos(~exacd}' in pf.Q:pordO[l to [S[ D]] (45'" cstl:aight lines .in Rg~m; 4,2!l1,nd 43, so tha~ [H+]] has tn c:ha[lgeonly cnol[]g:h to keep the k~.n. productconstant, Equa dQ:[I. (5,.2,1).

When a weakacid ]8 also present; a~: [h,ur] =::= 0.0(2" sothst [SIDI a~: 0.01 Bq/Lirer i,siw>~ [~.i'II'] / 2:, then dl;lnge>sul1 [ffID] c'aU$ec:hlllng~$ .in.][A] ~5'i)1,"r.;~~ ;15. in [OH·]. and [H+]m~5t tl:<ldjust m sathf), two cLJIui~ihl:iarnJther than. [ust one. The cotD:8:~)u[lding dl'.ll:ng~.~~fl [H~]I <life t]]erefore .litnch huger" It 1I100W wkes only m 25,000' suon.g ~.oi:'iswchange [1-e]1 hy lFI+,. This wte.rpre~atiJon of the [H"] buffer strength asa measu.,e ofthe u~mbe:r of Jl(" or Na" or Ct iO]]JS per unit volume that mus~ be moved into or out of a 8o]ution ]0 order to change the [H'] of th;ltt solii;it~O[l by ~ust .~ H+ ion is very iJ;i;sef~l.

These considierntions are also helpful .inrem:indiflg us tha~ [H"] bu:fCer serengrh isa dimension.le$sl])l']'mber, bec'aust; ill; istherstio .of equivalentspee JJtel:W equivslents pt;j~ T .. jo;:~. or ions per Literto ions pc;r Liter. pH lbufl'6t 5trengEh,. on t:he othC;if hand, has the dihleo~ .. il1[1s. of I[SID] O:f l[l\oT][I<11Ud.y,eCJuiv<l~c;nts [XI: Liter, because pH Us a dUhlcnsio[llcssnumbcr.

TVl{) a,dld.ld(ln!l!~SiS~'l-eCts of b'~Jlf,edl]g ~l~ay cause conf~snonufnot l,lnd!erswooun {&be context of allfour of the gum:trritJdvc: relationsh ip .. sthardefine <I. weak add 1;lolutiun.,EquJdo:ns (5.2.1) thwt]gjl (5 .. 2.4).. The fiest, often i.filp]vdt in. 4.1ltaJ]i~9Jti'Ve discussions o[buffe[~ng. is the

[B8,]

ahstnu:;( cOn1par]son. between how much H' has been adtDed. t:o~he solution and how much

[H+] ch:uJJg.es. ]f [H+]clls'nge>s b~r less tharithe amoun~ of H~ ~d,d!ed perunit vO~i,l!me, k IHay be suggested th~t the SoUUJil;!on has '~0111ehow ":fe$is~ed'" th~;;Ldded H", Asail.[e~dy pointed Ol,l~,. dlis i:c:!lsoni:ngigrlDtts the central fact th:.l[tH~us i:n.vDlvoo i[l . .t~1I1Cidnns., sl[]ch as water d~55.od.ado:ri. and reco:mbjtl.a~jo[J, so that we caariot e:-Kpec~u~ tD behave like s~rof.lgiolt1s that are not involved in aIIY reactions" There is no a priori .. reason to expect the change in [H'] to bear an:r simple 11;1sdon$h~p to the ~rtl0U[lIl; of' H+ ~dde& UnfOI:H1n~ll;d~?,·\J.;'ihen strong add is added~o ~. SI;[lOng acid sulmbn,. then [H~] behaves JUSiI: 1115 ifI-]~ were a stml1lg ian. Thechange in [H~] is just equal tothe change in [S[ DJ whiiLh inturn is .ius~ equ,al tothe a:d!ded H'. Carelessextrapolaeion from this special situation 100 solutions with p06.ir~¥e I[SID] values, in which [H"] behaves very different~r. h:[-espon8~b.Ir.;fOrmUJch Cl()nfusion in the a,dd·hase~ul(;~wr-e,. ]t is worth empha8izung tha~ eveninthis V~[y si1Up~.e C9S~ of s:t:ro:[Ig acids and n~g1l1dv~ [SID1 wlm:s, [H-+] ch1l1ng~s still C1l1[1~ not be un,d!etstoodl .i:f.I. tt::If.ms of Jr .. Wher.a. lSID] .is. increased, for e;l\1lJ:t1p]e"by add!ing s~rof.l.g !b1l!se inseead of SHOO,@; acid ]].0 H" is removed, ,ill, [il(:t~a minuteMuoU!n~ is addled, bll.l'~ [H"] M]ll fa]]s, I':-]ow Illuchand W~~l [[-]"]lfaUs; can only be undr;L5tood by e ... k~.ng ~nro account ~n~he variab.le5 and relationsh ipsi:[1 the solm~o:ri., not b~'I[loD~dng {l11l:~r 1I1t H'.

The ,sewnd. important confusion about buffering arises from failure ro recognisethar all four eq[UJ:ado[ls (5,2J) thlSough (5,2.4) must be s!l!tis!ied. EVl;r')' ollie of d1r.;111 is essential, [H+] is determined by I[,'\.LITL KA• K' ~\~" !I:[Id [S[D], not because of any s:ungl~: ,o:ri.~ of those f{~i[U ~G1UllJ~ tions, but becaese they must a]] be satisfied sJrI.iI.ulta[),oot]s1}~. The cause-effect relationsh ips between the independent var]albles. [5K Dland l[llT.crrJ and. the depend.e:l'It ones. [HAll. [A-], [0 H] and [H."] hiddea ~;way in the cubic equaAions in the Al'pend]x. and. represenred by the curves

in Figur-es 5.1 ~.nd 5.2,c~nnot be d!et:tlved feom ~r.I!y one of tile fbur S;llijtem-de~ining equations, but only fw.n(l all fUI[]:r of th~1U.EqI[]1I1du[l. (5 .. 2 .. 2)~s ofil:~n,~[:ttul1l,C{:msly si:I1I:~.oo Ql]Jt~b!t attencion as. most importaet a[Jdumefprered~o ~"hcrw how [Fl1 "depends on" theratio of I[H.A]~o [Al Since all duet: of tiles<: qU!a:l1l[](]es are dependent: variables determined by [5]DI and. [Al'lrr]~hey c"mnot d.epend o[l.e~.ch odlr.;r ~[Ia1'ly n'l!~~.ningfUJ~ physical sense, Eqru~don (5.2.2) can, of COUfS.e, b~reatm:[Ig'~d in s.c;vc;tal~mp th'.ll[ !I.[~ '.lln~CJui'l,."!I:~~,n[!m~t1~m'.l[[ic:ally:

[IH ]1 K_~ IUHA]I
[A ]
K [H ] [A ]
It IUHA]I
[A ] K", [HlA]
I~H ] [HA]

[H] [Ill] IK ....

T11'!::r cannot all be rrd.Hng us how one of rhe vari.<'IH.c..,depe:;ndis o:n.. the other two. Wli,h one is l"mt.rect'? They 1lJ]1 a[d T1-~e problem lies .i:Iil.i[l:nde:rs~1lJ:nd.ing clearly what this equation means physieally rather than. l1.uthe:w.JiMica]]y. Wh[~ irrells us is noe a single (;ause-dfe:ctre1atimufu]p. but father one .of~h~ :physkal,c01.1st"a~if]ts .on these three v:ari:ables thjl~uS imposed by the U;quiremem of C<j]uililbduttn. Any of the: above lio/tins of EqIJ]<1JJti.o;n. (5.2.2) mar obvi()lL"l~ybe:; used fo[ cn~ctd1lJti:ilig one of the three variables if the other two are known, Ibm 1lJ c1lJ1ct]btiOili Is not tile same as :it phrsi.cal cause-effect rela~:iOltsfu]p. Bquaeion (5,.2.2) must be satisfied arequilibrium,. buuuha.{is notwhat determunes the value of [fI+] nor [HAll no[ [AJ Those threequanrities <'Itt determined, in. this s.o:liIlIJtil1n., o:n.]~. br [SID] and I[AtmJ Theycannot, and do not, dde;tmin~ each othel'.

Tn view Qf'uhe very d.iffeft;nufu,eh!l,"1~or of wl;!I!k b~s~ "'bil;[ff~~,"'anjl~yzed in the n~x~ seG~io(], k is~n[e;tcs[ing to Sec what h"'[Jpe,m; to [OB'] in tbe'>ivc:ak m::H huffett's of this • sectinn, COi1np<'lri~ SOili of the [OFt] CQ]lfVe3 .i:ili. Figt]:res 4 .. 2andi 4,J w.ith thoseilil. Hgnres ,5 . .1 and ,5.,2 M1lJk.es i~ clear d]a~: the change in ItOfl] over the [SIDJ region areand IlSfD] = [~1T] ! 2 ]8, mud'! less tilan

k ~s wl1~n 110 wl;akaddDs pr~$~nt. If we were to c'jlk'l,ll!ll.t~ the slopes, and tlld~[;edl,)f{)cats,. by sui,cllly an'.ll~.ogo~s ptocodJ~[C.~~o those we used for the: [H+] and pl-l l:m:ffct strengths above, we shouldfind th"i! the [OI-]"]I ,L:Ut1leS are indeed flatter when we1lJknoeid Us. present QU1lJliudvdy, we eould cSa)'~ha(: 'a\Vea:rr:: acid. "buffers' 1[01-:[-] but not: [HI-J much better tha:l'll. water alene can do,

In 8Uil1rul'.llry, any solution with 3. pos:idve:; [SJD] w.b:: "buffers" in.. t:he:; usually implied sense thai! wh.e.ili. H" is added, t:hechange in. [J-['"] is less th.an. th.en.fi'i.0tl:ilit ofH' added pe:1f nn~t\ldJiJ,Itie., This property fo]lows fromebe dissociation eq!l:ihb:t:ium for water .. A well,1: acid added. eo sueh

!I! 'solu~ionre.dI,l!C~S its buf[a 5tn;ngih. but changes ll1~ [1':-]+]1 v'!llu~ around whicl1 k a[lp~a~s to buffer.

A wc:ak base, BOB,. partially d.issoci:ai!Cs 1[1. 5fJ.~ut:ion~o the: inn.s B and Q.I-[ A SO~jllti.nn. co:n..~ tlti:iliUili,g SU:O.ilig lens plus 1lJ \'ifeakb1lJS>e .. t .. tlY~:a] eoncentratien [Bnrr] must olbey,:t~ e~!U.mb1"il]filj, tile [0JlO\l,r:ing four equations.comparable eoehcse spec:i6ed [Dr a weak acid solution in Section 5.2..

(5.6J)

(S.6.2)

[8.S]

Consesvation of weak base: [D~] [ElOIr!] [BfOl']

(5.6.3)

(5.6.4)

Asbefnre, WC h'I.l:VC four simulraneous indcpendcm eGJuadons and fOI[];tt" unknown quantities, [BOH], [[H'"], [[Oft-] and [H'"] soweeenin pdndp]esolve for the fO!lu unknowns. The same kj]]jds of nlll:thema~ii(;:a1 ~)rotJk:r.L1S ar]se as w]~h aweak acid, and. the same llu.me:r]cal~echniques aee I),er.d~. a~ 'Q1;iI!tUn~d iii) the Appendix toahis C;h!iljl1;e.; The~5·1,1ltsa~ ~l~$r.;nted in Pigur-e,~ 5 ... 6, 5.7~ and 5.8,. whkh shouM be c:[lrcfu~.~y compatcd w.uEhEhe ptcv:h)]]S t.U.'1lC figUtt:5 aswell aswirh those 1:[1. Chapter 4L Va]ues used for these calculations werechosen tofacilirase thiscompa:rison, namdir. [BTOTJ .~ CUJ2, Kil ~ .22 X ]0-7 E~/Li~:eL, K' Xli ~ 404 X W-H (E~/ Lil~)~.

These :figutcs show thllJJt the dIcet of the added weak bese is p:tt"~mllJtt"Hy ovctthe [S~nD] tl1Jrtge, from zero to - En)'!'" A~ the midJpo.i:[lt: .of~hisitange,-[S.]DI[ = [[_~:\uTV2 = [BOH] = [B"]. [OH-I ~ KI) and. [H~'~ ~ K'\'/Ke. Unlike theweak )1Jci:d. so]utjjon, thisweakbase so~m]on ]:5. an effective [H+] bqJ!ffr;::r a~~hL$poi[lt; the [fI+] versus [5]D] curve ~,$tm.J!J:;hflla~rer ~It dl is [5]D] v~ll,lr;: (:,o.OTI EC]/Lj[er)~rtFigutt 5.6 thllJ[I.i[l Figu:tt"c 4.2. Siupe CgICll~';l[tiO[J~~ shuw th:;,tli: the fo:llowingl\bnnubs apply art this point.

L StfQng lOI]S ol]ly, fOif nr.;g!ldVl; [SID~ ~.III,l!~s;

(5.65)

pH b!.!!~fer strength "'~2.3 [[SliD] ~)q /li!ter

(5.6.7)

(5.6.8)

The n.I.MliliiJe:rsre:>l.dd[lg from JPpHCill;t~.(m ofthese formulas to our [Rn_},-][ = 0.:02 ElyLu~e:l:' wJuil:ion.ane presented in (:he table bellow. Most :5nit:ing is rfue y·ery large difference between the [H+~ bqJ!ffr;::r '$t:r-eng~h valll,l!~s In this; '~oll,IdQn and the",,'"i;~k ~dd soh.J!tUQ1'l jill,l!5t ool1isider-e.dl,. coma pared wu[h[he~de,rtijty of the pH 1:mff"et st:rc[lg:[~1.5 .i:[I. the, rwocases,

0' ....

I 2JJIE-2

~

3:' o .~

:~ ll,,0IE-2

~ :11:::

3 ,,0IE-2

'(l_O,E+1:D +---....,..---,....--:lIor-----r---"""--""T"--~r__-___"

'0'"0'5

"O}Ol SID (IE~!lIII)

f'r'

Of·r

'I:UJ'E+IJ -I--~~...,...~~....,.~~~~=------r--~..,..~~....,.~~......,r"""'~........, -(1',,(1'5

-0,03

-'I).,iI11 ~HI (l~igl/l!l)

],,0IE-2

~,

':::' ='

1iiI! 2JJIE-2 -1---------- .....

'O-O'E+ I:D +---....,..---,....---F-------r-----"'r---""T"--~r__-___" -(l')J'5

F~glUire 5.6,. [IWJI. [[OIH-][ [[BOIHI]alfild [113"] ver;sl1.[s [SIID][mr a single wealk b,ase solltlllllo:fil wiltlMl Kg"'2.2: x 10-7 ISQVL .nlld [61"00] Cl 0.0012 IEq/ILJlie:r. K',.,. Cl 4.4 X 10"1~ (EqlU:er)2. IEifilllargedl verttea I salle Ilnltlrne mldldllle: graplMl to slMlow lM,cyw [IH~][ aln:dl [OHI-] vary with [SliD][ ovell a raln:ge: flmm -[~oo][to' 0,. 'OOIi1l~ pare ~y~tlMl~,gluJi1e: ,5.].

[87]

LOE-O

MH~ S"',i HI''' r

LDE-6, 'Ot;l' (""1/1) LOE,.o

~OHl

FiglUlfe 5"7,, Lo'I;:Hlog IPlot:5 klr the salme SiollliJ~ion as lin FlglUli',e .5J5. GOlmpltllre wlltlh fl~liJlt1e S.2.

-l.O

IN,!) we<3lk Ib<:tse;

[5m]=-o.Ol Eq/Uti:er

Wealk bacs€i,; [BrarJ;;;;O,()2 [5[1)]"'·0.01;. 1KJ!.",,2 • .2xlO-7 Eq/lll'be,

0.023 Eq!lLitelf

TI1e d~f£e[etl,ce in the [H+] buffer strengths is Jlt]St opposhe to whalt .ilt WalS, in the wealkadd case. Here.jheweakbase sohu~]on ]5, abener [H1 huffer by a L'OCtm of 25,000" whereas inrhe weak acid! case.the solution w~~hout \,~ak acid w,as:a beltrer [H"] buffer by a. faceer of almose 100,000, The pHbuffl;t' Stf:el)g~h entries hl;l"e !J!.1fe kiel)iI;kal eothose in the ·'m..-""i;ak ;tCudc!J!se, despiltc; the; hlrhl'C dliffc;ifC;ncc:s in [H"'] lbd.1.~.\7int. This ]c:~d., 10 the g[J1=l~;renltlyco:rlt~d!kmryGDn. cl'l1sions~h1l!tal~h()ugh itis 2'::',.000 dmes better as an [Hllbuffe:r, the: weak base solution is ml~y half as good a pH buffer:lis the strong aeid solr'ur,i:on witfuou~ weak base,

In the gin~e"vc:gk gl:H GIS.e, \\'Cliound[ha["[OI-l] huffcri;ng" wasneuch better thgn in. 11 strong ion olilily 30]ndon at the same [S[O] value. Inthisesse, a silillgle we1l!ik. basesolnticn, the opposiee is true. This sO]UJt:.ion ]8· a better [H"] bufferbut a W'O'l'Se [OFt] buffel~hai!1 a s~rong iOI1l only '~Qlu~.ii.on at the same (l1I~i.VI;) [[SID] vah,lLe. SQ fa," as pH hufferi;[lgu~ i!;or.l~e~r.ll;d., bo~h

1\0,1)

8,1)

6,1)

:/:,0

O,O~------~~------~--------~------~--------~------~

-I)-O~

-O,O;l

-0,01.1

e,·(1~

F~!1IIUlre 5.·8" 1iIMie p,1H1 VElIi'SUS [Sin)] cJ(jlrve~or ~1M,e: !Oolu~l,on of IFllglllJlli',e: .5.'15", Com p>are wlltJIil IFlgures 5 • .3 <llndl 5 • .5.

weal;:de'I;:~l:o~y~e '$ol!.,l~jons~u'" worse pH b~:ff~~s than ~. stl:-Qng ion only sohrtion.

The concentration of t:he \v:eakeileclTolrte del1cly affei;;:l\Sa. solutions buffer slI:!Cengtli. butas lAnci'll'~ or [B'rl_i'II'~ becomes larger, so doesthe mag;ni~ude of [5[D]1 al: lite I[SID~ = [~)''i'] ! :2 or

~ [8][D]1 ;;;; [13m,,] /2pQin.::.The [[-1+], [OH-] ;tnd pH Ve.I:Si.J!5 [sm] CUI'Vt;;S aU 'bero~11eflan'el:at th~5. point, ho",re'!lcif, s.o th:1lJtbllffer sttcngil:hs !llIi:!lJcifc:!l3e w.ith i:n.cte'il.si:ng I[}\TDTJ or [Bl'Cfrl The fa[fim~M fi,)[ lb~lfmet stfeilig:dts gi.ve:n~n~hisa[J,d~he preceding section all show this ,ef£ectd.ea~.y when [1\'l.nJI/2 or [BTorJ/2 are subseitueed appmprill~clr for [81D~;

[AID!"] 4K",

pH buffer strength = 0.6 I~Awr] IEq /uter

2. Wel1k base wlm:ioll at- [SID] = [BWITJ/:2:

[CHAPTER. S - WEI'oK ELECillitOLYliES, MIl IEh.lFFE~S']

1[89]

Because of this dependence on. [~YTll1l!mll[BT(nl .pHbufre:r strength is sometimes divided by [l~OTII Of [Bnnll ~ndc~lled. siml']Y "buffer s:~!!ength." or <'mD]~rbuffer Mrength." From

~he abov.e f{)r~1ilu~.as,. th is CUu~t'I~UW is 8imp:~r 0.6 (0.576 to three signi!:iccal:lithgui'eS) ~1:1d d:h'llt;nsionle;ss, :aM1HUgh i,t lUay be describ ed as [Hi Eq/Litc;t [SID]ch;,ttliJ:;C needed to pro duo: !I. pH cha:ilIg:e of 1.0 1.r.'11 a weak acid or wl':a,kb:ase so~utio.n ~J a wm:e:n~lf:lli!i,o.ilI of to E~/Ute[.

Anothe~ r,,~nl!:[e Qfweakad.d and ""'eai:: base S{)~U!.dO:t15.fb~.~{)wc$ frll)~ll this :;ma~ysus,. In a weak acid SUh:lJtill[l. with [3:]D] Set lo [1\IHV2, [H+] ;::;; KA and pH ;;;; pK A' In g we>JJk base so]utbn V./~t:h- [SrrD]lset to lLiBT(}T]/2.ILB~]1 =K'~KiI a:[iid pH= pK·~. - pKiJ' We ciJJn therefore use eu~het a 've~ka~id solution at [SIDII ~ [l~OTI ! 2 or a weak base solutionat I[SID~ .~ - [BTOTI ./ 2.~:o m~ikr;a"b~ffei['" csdution <l!t ~.t1)' dt;5:~r.e.d [H+] v:a~ue si:mply by i;hrJ.O;iJng a 5·ubstal:l!Ce w~!;h tht; :appropdate K A or KM,V;,l~ue. Once; I[SJD] is Set to the rulidpoiiIJt V3.ll[]c of I[j~rr] j 2. or ~ [B-nrrJ j 2. thenir is notwbetherthe \l,reak electrolyte isan acid or a base thiJJt determinesthe [H~]I value

of tile 5O:~!,lIJtion but the numeeiealvalue of the dissociation con5t~IT~ 'cojl~pan;d to JK '!Ai. The convennicnal tel:ttr.1.i:[Io1Iog}, may confuse rh hi jSSJllC by S'l]gge:s:ting that it should be weak acids that lbufffiet strong bases and weak bases t1:llt buffet stW[iig acids, It shouldbe deal fffim~he preceding discussion that the "buffer" is the whole sohaion, :[!jot JUSt theweak electrolyte, a[iid the role of w'ilte:r is at least as itup():rt~ntas dl;at of ~ny otfu.er com:pDj]jen:~. In ['act'. "buffenng' is aproperqr of the "",thole sY's~ln,.al:ldkis n'lJL~~~ung to!I~tdb~te i~ to ~.ny csi(]~e c{)mpon~n{"

A. flleque.lli.dy used term]nn[ogr to refer to the [S[Dllvalue ]05. "bufferbase," The ideill behind uh~S~erlnDS that the netexcess 5UOng 'b~re, wM:;;his just jhe [SID] "",lb,en I[SID]D5 P05utUV)l:, cs,peci~~e:show tI~lllche~ect:['k:~~ cspaceD5 ~vaUible fo!t' weak add (~.nd theLl;Jo!l'l:;. sUl')po®ed~y. '''b'uf;' fi:;t"'} anions, The dift.ncl[]~[ywith tbis ~fmi[l()log)' isthat .it: i:g[lo:~:e ... thejmporranee ufbothl:he; v.rater a:[iid the s.tmng ions and St]~-:ests that it Us. the wl':1l!k electrolyte that does the bu.ffed.l'I,g. A mme accurate term tfua~: is cfrenused di]'ljjc~]ly is "baseexcess" or "base deticit,' I~ refersto tfue d!r;pa~wre of I[SID] f(1)t.Il!Jts [JJ(umal value. Theterm ''':a(]~on gap'" is ~lso Of[l;11 used, \V/e ddr;!t' mOltl::detai~,m dis.cu5s:iofl of these [e~tms u:m.i]l:he; effects of Co.2 harve been ;,ttli.:a~yze;d in Chaptees 6 iJJ:i'1d 7.

Inprinciple, noehingnew needs to be added. to our ll:i:uJy~]c~lproced~ in order to und~~tal:ld q~antit~tiye~ra csdution oon,tainingbmh a weak ~.ddand a~",ak b.ase. Q.~ in f!)!J;;t any [JII[]111!be;t of'cach. This is !I:Mther point atwhich d)epott::nd>JJ~ >VC1lkh. of'dctail mentioned at the beginning of the C:hap~e:1f:itppeiJJ:IfS. because eachpardcular case requires its own spec. tic >tqtla-

1[90]

'tIJ1LOiE-2 =

irj

'":c: !I:UJ!E+~ -l--~......,r"""'~"""~""'::Ior-~~,....~......,.~~..,...~~~~......,~~....,.~~

-(11,(115 -(11,,04 -O"O~ -0,02 -0,11)1 11),,00 (11,,01 0,02 0,,03 0,04 II),II)S

SED fEq/l)

~ ifi"OiE-{ o 4JJiE-i ''tIJ

,~ ;UJiE-7

~ 1I),(lIIi+O -F~"""'r"""'~....,.~~.,...oOIi!!!!~~-----r---=~~-"""~"""'~~"""~~

-(11,,(115 -(11,,04 -O"O~ -0,02 -0,11)1 11),,00 (11,,01 0,02 0,,03 tiI,04 II),II)S

SED fEq/l)

f~glU!re 5,9\, [H"] <lll1ld [OIHl'] VeltSllJlS [SIID] for <I solutl:on co;t1lt<l,~n,llngl both the WElI<lk <l,clidl olr iFIIgllJlre s.i and the weak ba,se: of F,lgure S,,5, The: v,e:rtJlcal sca,~e: lin th,e I,ower Mlr of the figure has been et".<lPande.dl 'tDsh,cyw how [lH"]1 <l,ndl [OH'] be:have "'''leI! the [SID] li<l,ngle 'rrom - I[ByoQT] to, + [AQTJ 1Ilhe hOl!li:ro;t1lt<l,~ !scalles for [51 !OJ are th,e same, all1ld I~ rl:!g~ster,~or IbotlM!glraplhs",

drn15,w,itlJi irs own set of [~)ir]I" K A' [BTo;yr]1 and K~! V<I]I[]C:5~ andits OW[lpai:ticubt grnpb.~. ,Malliy pagescould be spent expleeingtbe hrge ur.lhretse of 1l!H such :systems snd their acid-base properties. It will suffice ro point out: here ~:h:a~ each \,~ake~ectroJyte aad,s two additioeal ,ifllle1'tudor d.et1~t'ld~t1:t v:-ari-abl~s,~ts [HA] ;t[ld [Al o~ [BOH] ~.nd [B+], Qne!lldd~iI;kmalextelf[lany d~te~i:ni:[Ied ott" ,i:[Jdcpc:ndc[Jt variable, [~)11":] or [B~)I1"J Q[lC addidonalparameter, K A or KB> 3[Jd two neccssaryadditionalequatioas, either

II:H·~ [KJI"IK... [HAJI I[ inA] + [A' 1'" I[ATOlI" I

[113'+] [Otnl"I~~ [BOIH~ [13+]+ [BOIH I'" 1[8Mr]

io.,iHi +----___,O!::...------r-----.---------,---___:~---~ -!UD3

E: '(Ul'2 -1----- ... 'ei" WI

t~t

IHLA

".:c:

,'= :t::::

I~

~. '(lJJ'l

io.,(lo +----___,.t!!:._------r-----.---------,-----=:!Iiot----~ .llli;D3

IFilgul!"e' 5"110,, [[BOH], [18,']" [HA]and [111-] versus [SIC] tor the S<l,rme so~utlo'n as lilil F~gure 5.9" C~;mf!~o;,r1li: with Figures 5.1L <lll~-UJ 5.6.

TI~H'.': addkional ionic species, either A' or 13" , mast also be included in the eleetriealneutralfry eguat]on, whichtherefore becomes correspondingly longer, So. far asthe cakubti:l'lg proceduremcrodaoed ,in the Appel:ldixH) Section 5.2 is ooncem..;d, th:us increased OO~ll[l~exhy is easHy

WH,. B'~';I! Hl+ r l"OI;o~, OH' (Ei:V~) 1,0;1;06

LDE-!}

LOI§-~

LDE-1D

f~glu!re S.ll" Log-log plots foralill :ob:: depeil'iide!l1lt va!l!~al:l,le versus [5[0] foil' tlfl!!~ sO~!I.~tlion! ,of Figure 5,~, Compare wlith iFlgures 5,2, ,5,,4a!l1ld ,5,7.

hat'ildled, 1l!:fid. tbepoocedute w~.Uahv::iYs gi\le us' num'iLbets ii:n.d. gtil!phs 1l!S desired,

The~$u.~ts of 5uchc~lculat~ons fur ~."athr;r 'siinl'}:~em~xt~:r-e, a s~[Igl~ we~k!il;dd and a 5:iiflg~r; weakbase, with the same [AroT], [BmT], K .... K~, and [(> 'ill" values as used :~nl:h;:; three previ-

ous sections, arepresented I:n.. Rgt:ltts 5,,9, 5.10, 5.'11, ll:n.d. ':;',,12. These fjgures should be care[ruDy compared wirh their counrerpartsabove toappreciatethae theacicl-basebehavior of ehis ~ub:tu[-e is iflot .i[l.an}, sensethe 'Sililm of the beh:avio:r.s of the ®ep<lJ:'ilI:~r; weak add and ·wl;!l.k bsse So.~t]tjDn5. The: pre."e;no: of e;ac&!Jwcal>: de.ctro~pk pmfouDdly gffe;ct5 i&!Je:khgvno1if nfilh;:; ot:&!Je;if. TIle effect ofHA is no, longer restrictedso pOsiut~"'e [SIDI vll]l]eS, [io:J[ isthar ofBOfI restricted m negative [SID~; bothweak elecerolyres are involved over the full [[SID] range from- [BIOT][ to + [~}"l'l[. As a resule.rhe special properties of the [S[D] = [1'~1!]'1[ ! 2 and! [SIDJ=- [B-nYl'I[ ! Z 1':IO~[Its a~r; [I)(} longer 1.:Jir-eS~l]t,

Such mixtures are much eeo complicMed. to thjnkabout q~aJjjt:at:ivdy.We can Dlllyan'S"\'~r que,Stk)1.1sibout dldr b~h~!"l~o~ by being !lIWr;~o caleulase .~IJ;., 'Ill.at is why th~guandt!iL~Uve <lppmach isessenrh .. L It permits us to understand such 5y5ttl115 by Clllcll~.'illting lIfldplotrring rheir khgv101t. In this :p![Il:t.kubt case~~harr behllviot seemsrather gjtll:uple, but it should be !tt"\:cogn.ized thai!: rtli is 13 a V'err spedal case I:n.. t.hai!:\I,:lt ha.\I\:::cho3eii ['\0"]= [Bnn] and KB= K' 'II' ! K A. These s:pec]a] values ll.COOW1.t:, llmorllg other t:h:ings" folt' the synill1le·uy of (]:]ecurves in Hgur:es

1[93]

(1.'0' _----~----~---~~---~----~----~

lFiigulile 5,,:12. p,lHl 'IIlllf'SIlJIS [SIlO] riJ:rtlmesollllJll1lo:rn of Figure 5,'lt Comp,are ""lith lFlgures 5.3, 5 .. 5 allll,dl

.5 ... 8 ...

5.9~hrollgh 5.Uabt'Yltt the I[SIDI = 0 point, ll:[ld. mila}' besomewhat fi'l.~;s~e.ad!ing. The gerJ.e:r:a1 !611Se au] he as oomp]ex I1S y'O!I.l wish 100 male itl,

5.8 GIAJMIBLEGRAMS

The prepereies of rhesevasious weak eJie.(;:rrtilY1:t: solutions may alsobe looked ;a~ ]fi rerrns

of gah1lb~eg~i118. A. vel~ywide variety of them could be dr;lWll f'Qr a w~derca(]ge or [SID] valiUle.s in. ~!I.ch 50]m:bn considered 50 [gr. The tt1l!det is ufJhrodl~o draw lots of them as :.lin informative esercise, As illustrations, we ptese:M four ofd:iJemil!\o1f t:I:iJei:m:eresti:ng points [SID~ = [A,-m]1 ! 2 ill eheweek m;id solution and ill the mixture, i1J]]d. lSID] == -I[BTJ;)T] ! :2 inthe weak base ool~~ion. and in the mixture, These ;J!;~' ShO'l.ViD iII Flgulll' 5.13, They \$ho:u.ldprovk!e :;lq:lsefuJrevlew of

!I.n the pte[~ding 1I!rtmlysis and! di,cussbn and ibioul.d be ~!lsHyllmdcrs~ood. U[I. tbieb!lsis of th',[[ a:naJ1Ys;u3 ..

Si1J]~S may be de1imd as s!!l!hsrmx:es~ha~ dissoeiaee in i1J~.lJOOm solution t~pa:ir,s of ions oeher than H+ o:~ OH-, TheseiQI];$h1:;lY be S~:l:Qr.lg or weak,. 5Q~h;J!t dlr;~are four cases 00 considee,

~ID.>!I·.'iI""t l_.'.nd .... __ AoId lRll~",,s.8)

,""",~le;",~~ ~Flgure ~4'

-

-

_."'Old""'tr jl'l~u .. ~'i)

·cr

~'"

I>!l!"

er

v~" /Olf Vii' /af /t1" /CfJ1' I/il' pl'
·Catic.ns ,jl,lIIi.:;ms c..~iol1ls AniiOClls C;liil;)ns Ainil;)ns C~'~i~ns ,jl,nliQ:ns FijgllJll"e 5.13 .• Gal11ilbllegl~ms ro:r selected :spe,cilfh::: [5[IOJI val111lles in the sollutio:rns QJ Fli.gulres 5.], 5.6 .

• and 5.S!. In odler to SlimlPl~ry the liiglllllre, only [Nail and [ell"]! halve been usedlltQachi:e!Ve desiredl I[Sm] valllu'es;, In alill eases, [fit) ~nd I[OIH-) i,'ll!i"€ :too slmal~~ to be seen 'Or1, tlhiis '1fflIrtiC'allscale •

. ~, lfbothuons ;J!:~ 5tl,l;lng, t~r;:;n~b,e sclutien h dir;:;s-crilbr;:;d. guantit;J!dvd.y by ther-e~$Ii,J!~~5' ~,n Ch~pte[ 4, wkh [SID] ;::;: 0, It will beacid- base l)eut~L Such sobiot1s ~[I,fs,(;~ ~:re iI)ISU;J!Hy 'cail~ed "nel[]ttal, sah sU~l[]iions" evenli thouglli,. as g]re'illdy ~[[TIphg~'Si,z.::a,[herdo not (!o:nlit:aitl, lIny '''s1I!1t'''per se, lbmo1nJy ions, Obr ..... ious eX1lJn!lip~.es are NaG or KG dusrolvea, inwater,

2. If t~'::C1l!t:ion~5 strong, hut the g:nlibrt \.'\I'I:.':1i.k,. th~.n the solution bi:[):disting~_]:~5h1l!hle from 11! weakacid solation with [51DI= IlAtotl. The-analysis .of5ectio[lJ 3.2 and 5.3app]ues 1lJ:tld. shows thai! such 111 so]m:uon mm,!! bealkeline, with [H"] less than [OH.-I .. I[lJ this. case, thecubic e'lllladorn for [H +~ reduees to

[H ]

K'w K", [ATQTJI

This means t:hll~ asehe ,sal~ ecncentrasien increases. [H'] decreases, the solmiolllbecomes more alkdine.

3 .. U the cation is v.re:ak a:[lJd the a:[lJ~oti s~ro[lJg, then we h.11i'1e - I[SIn~ = [B'nH'] 1lJ:na. the 1lJn1lJ]Y:>u:> ofSe(;:~io115.6app]ie:s, lu~his ease.jhe eqmuioJ1ll for [H'jbeccmes

[9.5J

K'w [STaT] K~

(5.9.1)

[H ]

This sobuti.on becomes more acidic as mere salt: is adld.ed.

4. If"lboi:h Clll:ion g:n.d aniori gr~wc:!!k:, then [5]D]1 ;::; I) beeeusethcre ate :n.o sl:tf)(n.g .iDnspifesern, J:[l!d the etIllatDoln for [FI .... j becomes

[Ill ]

(5.9.3)

This tells usthat whetlle:r the SO]ll!t]on ia acidic, basic, or nentral depends only 0.1:1 tile rnt.io of the d~s~cH;::latkm con5tan~s.

We assumethroughcut thatthe salt itselfis iLt'):mplettly dissociated in solation .. If that is nor the case, tilen we musradd anether eqw]ibrium expressioneo our list of equsrionsaud another V>lf.~~lble,. th~cot1Qr.;nc~lo:n .of undHS50datt;d salt, Thel5t;us nopf{ib.leln :un do~ng th:us:, and OUf numerical t:c:cJ~niqlJ]C:8 w.i]] conrinue toptovide 1I:n.}' d~8~ted ca~clJ]~lItio:n.sl\bt such :.lI. S;'5t~ln. II: is usmdly~hec:;t:>e. however, thalt such salts are romp]etdy dlssoclated, and the only e~llj]~br.iaJ We mnstaccount for are tile \V'Mer" weak acid, or weak hare dissociations.

In ;o>umma:ry, sgk~ of weak lIdd!s o:tt" weak bg~ s es, when d.bsoh .. 'LXlI in. water, do not result in acid-base :[l!el)iUa~ solutions. Salts ofst[Qn,g bases J:nd. w·eak acids have ailkaHne :>oh.tth:1:S,. salts of $~rong acids andweakbases ha:\'e aeidie soJu~:ions" and salts of weak bases and wea.1k: acids may have ~n~hr.;r, d~pr.;nding on th~ values of thr; tWO dis50dadcln c.'Onst!l!n.t\'l.

Uli:h~[wn forms of a weak electrolyte hll.v~ d:~ff~[~IJI.t cub.rn in sdlldon.,[h~n the c{l~fJ(tt" of their 30lu:uon will change as [S~]D]I J:[l!d thettiore [A-~ l [IlIA~ or [W] l [BO['::I] dw:nges. BOC1illSe [Fr"j also changes with [S[D] and there is a. ne:cessaqr correlation between these ratios a:[l!d [H1 becaase of Equation (5.2.,2) or (5.6.2),. (i1e color of s-uch lli. so~mion ]S llin indieseor of its [H.'+II. Th~Qr~~kally,. ~il; &hQuld no, m!I~!;,e1: hQ'l.v rL'lJ!I!ny Odl~1:' d~cil;l:-Qlytl;.s ,u-,e prr;sent.; they Ganrnmailtel: thevelidity of I:hos~ c~I:I.:.lI.[i,oiIJs, In practice, however, the pr~sc:,nG~ of sped tk sulbS[anG~5~ as .ve.]] as. cha:n1iges. in total iO[l!:icGOI.n~erJ~,. may aif["ect the value ofK il. or K,~ for ai:nundkaror substance, and. ecrreceiona nlay haveeo.be made for sueheffeees, A selueion with an indicator. added is lli mixture arnd cSllouM be an!l!·~F;.e.dI in. thr; t'el':I1'lJS ofSr;ctiolJl 5.7, 'bil)lJt 1)lS,1,l!l!Jly~nd~C!l!,i;{J(r substances gtei:nt~nsely w.~(Jtcd., So thattheyneedtobe ptcscm lIt on~y vc;tt"r small [i\"lYr] {1[ [B:l'L)T] '!lg~IJ]C:S:. Theireffects on. the other wt:Jk dect[0~ytes,:;tnd specifically on the [H~] of the solrtlJtio[l!. Cll:[l! therefore usua]ly be ignored.

[1Pl'iRT ]_. lHiow TO 11JIINI~BRSTANU A.cm-Ei.AsE, STEWART'S, CLASSJ.C liEU]

iJQive:r]ng~heWihoJe useful range of I[Hl The}' filll}' be used in lieu of pH meters for:.ppro:xiillatemr.;~su!;eiIl.el1J.ts al1Jd aee often cslled ·'~')H hl.di.catO!ifS.!' Hist'(uki~~r,their use p~ce-.ded by i]ljlH)T yt;~r.$~hr.; gl!il.s&-d~ct!'{J.dJeelec~r~n.k ~l!illp:1 if.ier pHme~r. "pH p,ap~~" ~:~CO:lni1~r1;ia:Uy arv:aiJab.k, inlpregn.;i[[cd with 'il series of selected i:ndkaiCOItt"dye:s.

The [H+] (pH) of an unbno'Wn 5O:~~dol1J may be e$dm!l!~~d b}'mOiL~tenung a small strip o[~he pgpC!tt" with IE and comparing the n_'~oltt"D!bE:.'Iined to 'il il:&"i::tt:nc.c dlilltt. Such i:ndiC'iliCDl: subsranees rul'il}' :.'I:~50 be used to esi1i111atc:: lIB") in othctwise inacce:s:siJh~c sO'lliEnons, such. :.'IS inside cells, p:1fo'l.dd.ed! K A or Kac9i:n be assumed tD be .kncrwl:'l. in such :l.al!UJtlo.[lS" The resulss havege:netnl~y been wn.t:royersia~, .however. and the indirect procooure described mthe fo]lmvlng secriea ]:5. Il~fr;n:e.d.

Indicators haue:>!Js() wml'iJbu~ed eo rhe wides~)lddm:isun(Ders~anding of the meaning of E~.IIM~iai1s (:'-2.2) and. (5.6,2) •. relating [H'+'j~(} Il FlA.] ! lAJ or llO [B+"] ! ILBOH~. The iirseparsg~ph of ~h~s '~r;c!;k~11J ~llight be lIIisiif)~erprr;t'e:d w ilJld~c'!lllr;~h~t if dl~ ~l]di~~Qr~s ~'Ufl~ci~[Idy dj]m:c. then. the other dect(;J:)lytes i[l. the: 5o.~mif.ln de:Jocrmi[lc I[H"] and [[:.]: .. ] in tum dete::tt"rnines [HA]/[A] fDit the il:'l.dkJ~or. It is ve:ryimpo.ittal:'lJt to t]:[ld.e:l'Sw:[ld that thisis not the ICJ:se, .. his the: value of [SlD] d~alC deeerminesthe values of [H"], fOfq and the [A-] and [H:Ars fmall the weak ~d.ds in tile 5O:~l,l!dol1J> givenl~xed v~JUt;;sfbf.'!lIJ~ the [1\.)1']'5. A.$ailre~dy di;~ciJ;i;~s~d, dle~quilub~iumroql(]:ircmciIJt fQ;tt" HA dissnciaEbn,. EC);rulti.o.n. {5. 2. 2). tdl'l us how these .tesuli!i:ng: values IIII(]St be relsted •. bu:~u~ does l11.0~~d.~. us ]]0.,"" t~er J:re determined pbysi.cal.ly,. "The coloe ohhei![ldkator therefore tells us wharthe [1-]'+]1 is, but :it does [lot (De~:erm:i]]e the 1[1-]'+] nor does (he 1[1-t]1 deeeril~UI1Jr;it, They ar-e both de!::e~mjif)ed b~r thevalue of [SID]I .

Ifthe undissoeiatedfoem of .. vc:gk :.'I.dd 0':[ wealk hilseis~ipjd s{lh]Jh~c,. it canbe e,-xpectc:d to pe.mileatemo6~ cell memlb[nneseasuly~ even though theioniaed form wi.n p[1~brab]rbe: imperme- 9ibk At t:qt]:u]fbrJum; if t:~e substance is t'II.Ot aed\le.~y metabolized or otherwise processed lby~he cell, the concentration ofthe undissociased molecule should be the same.inside and outsidethe cell, If'the dissoeistiee ClQl]s~~n[c~n be ~e5s'Ul'lwd1 to be t~~ S!l!:l'l:1ein~mh schnions, t~is equ~l. kyuf [HA] or [BOH] makes .it possibk~o e:Si1ilJrl'iiltC IIH"]I inside the cdl on the basis ofrcJ:.'Idvdy :simp.leconaentti!1tio[l measurements.

To d~nRmM!f.;l!'W: the a~glll:l11eI]!t, SiJ;ilppOS~ d1J;l!t '~'l; have 'aknO'WB vD11,uI~e of cells '$us.p~:l1Jded :~n :i1lnow.n vO'lUh.1C of su~miort,. and :.'I. weak acid, llA, which isnotmerabnlized hr t~cGd.t'i, has

J ll:'l(lwf.1I K,c\ and e:m:e:rs~he cells e:as~.~1r ~.f.1I. the formFIA We:;tdd. a k[lo,"mwtn~. amonf.1l!!, [A~otll", ofHA eoehe cell suspension, mix and 'Wi1I~( ['Or eqlil:U]ibrium ... \'f/e [:hen analyze an a]iqll!ot ofthe ~:;::~mal SQl\.l~bn f'Qr its CQ[lc~lT~~jdQI1J of HA p~\.lS A-, 1[~'YIr]I~.!il.if)d~t);l [H+]g. ~F['Q~ll dl~,~e~wo values, rhekaown K ... value, and Equatioes (5 ... 2 ... ~ and (5,2,,3),. we can C'illcl(]btc: [[.'lA]11,i and [At,; 1[1 t~e esternal 30ln:io.n. \Ve 91130 analyze an a]iCiiU.o~ of the eel]" for thei.[~ma~ oonte[lt ofHA. -+ A, call r~ [~n]i" .As.suming tha:~ [HAJ" = [HAll], we now knO\l,7 [~J!"][ and [HAil' so we can calculate [11..-]. trc()ill ECJUiI~ion (5,2.3) and then [B-1] fr~m (5.2.2}. Akemadvdy, 'b~cauc~e we Imow

[ft1U!"]lL and h~ye measured [~)f~t we can calculate [ftrm . l, ]OSt:ea.dl of measuring it,assmuing none of ~he Ol:uginllU}' ~dded HA ha;s beenlost,

A ",veak basewould ob\douslr work Jmt as well" whh lipproptia~e subsHmtno.n of VlilfUlib]es. and equations. Ideally, the M~bstall(e used should be easily measured ~~~veqr low concenrrations, OO~h~l ~d.ios,'cd'ill;ly l~beled,""",~k adds or bases car"€: atii;r:acdve c~l1dudate8, A vaf'j,e~y of sub5il;anc· CS is [1;.<;'00 by differem .~>JJbotatm.ues, and thercsrm]ts o!bt:.liJled g:e;rrctally indicace that in~rncdhlar [H"~us S{lme~la[ higher than estracellular, bur that diffi:.rc[lJ! cellscan be vcty diffi:;[e[lt.

In Seetion 4.7 the process ofd~rnd{Mli. was described as a systenili1l!tk changein the [SIDI ofa solution brought' about by adding small ~mo1l.l:uts of s:~rong acid. or s~rong base, while measuring [H+1 (pH), until a.cid':base nr.=utrality i,s ad~ir.='ill;d" ]n a SOhl!il;ionCQ1.1{~un:~ng on~y Si[:ri)ng io(]s, this procedure yDdds ameasure o[[hc otiigiJI:l1 I[SID] vshae in. the 5dlllJtk~[I. NCllli:rn~ity is e:lsHy idc[I.z titied hr virtue of the large li:lrld.rapnd pH chaJnge near that point an the pFI versus [5]D]1 curve,

As Figur"€: 5.3- indk!I~es,uhetl;are' th:re;e inte11;sdngpQinJts on the pH ver·SqJ!S [SID] CUI'W'

fot a'<vccik :I.dd s'{lll[]tiu[I, nor ~ilI.:st one. The I:tl.i:st is ;,t[ [5]D] ;;::; 1[/~']1L)'F]whctc;[he pH (but not the [Fr"n goes~h.ro'Ugh.a.re.btlvely b~-:e 1lJ,ndalbrupt cha;nge as I[SID~ passes th:rotlgh. h. Anothelf is

at: I[SID] == 0', wherethe same t:h.ing happens.Here also, there is nmhing in the [H"] curveeo o)nes~jQnd to the pH behav~o.; The third pointis ;1)1; [SID] ;;;; [Ann.]I!£: where, as we have seen in. Section 53, pH: ;::;pKA {lit [H+~ ;:::; Ki\' Ndthe;r the [H+]rloi["[he; pH: curve has any~mJ:[I;;:lh~e featureat t1uspoinJt. ~]~is simp.lr ha~fway from zeroto [~Ol'~ on the [S~UD]I axis, Because the b:rSt'~WO ofthese three points may be easily iden~ified on. the pH vers-us lSID~ curve, and ehe

th ir-dju8 just halfway between them,. th is curve pe1tmiu. usto estimatethe values of [A,"(),,], Ie .... , and the otu.gin'.ll~ [S[ D]I valueinthe sd.mioG. if these were not ik[lo'.vrt. An ofthis only >JJpp~i.cs, ir must be noted, whell].onll}, li s<ungle weak add is p:resenJt. Figure 5.6 shows that cOftespolnd:ing infoemation about li, s;ungle weak base canbe obtained from the p[::I d~rnJtiolrlcu[ve of lts solution ...

Inthe solution conJtal.ning more than fJo:[IC weak decn:u1rtc,. -ort[hc othe;r hand, the: pH curve p.ny,.ides\leq! littleinformetisn, Large and abrupt pH changes !C1lJ:n no Longer becounted onto show up a(: the 1[5rD] == [~H] or I[SID~ == Opoims, ai1:ld~he~e is 00 \va)' llOi.del:ltify K",'s or KB~S. l'it~idon .Qf ,s;~ch a ~llb:ed 'soIu~ion oonr.=uti1l1j~y {pH;;;: pK" .,J2)m!l!Y pn:wMe a 'Jetf}' ~~jpi'"Qxi~1ilate tl1e"asur"€: of dl~ o~igjni1IJ [SU1]1 in i[:he sO:~qJ!donuf it is a;s8umed, thll~ [SID] ~1; n,e~tral i!;)ris reason· :lhlv close to [5]D]I' ;;::; O. !bl[]lt that mav be a verv roueh c,sti:[[I]>JJtc ~:n. some eases, The tc;r[[l] "titrer-

,I" . ~ ~ ... eo

lible acidity" is often used in thisconeext, It is usua~.~~! definedas the 1lJmon:m of strong base dut

must be added LlO d~e solueion ]n order eo hring the p,H. to some ll,rbf~rl1i1tY value, oftenth~t of stand~:~d arterial p~a5Ina,pH 7,40. I;t is th~n inteq:l.r~t'ed as ifut wer~ a measure of the ~inQU(]lt

[!if H"ptt~n,t in the f).rigina~. solution .. "lllb completelyerroneous .i:[IJterp.~tatbrt seems tJJ have arisen historically from the equally erronecus notion d]1lJt H~ is :a stwmgnon. like K"'., "Titretable aci.ditf' is a measure of how much [S[ DJ had (:0 be ch:i!.n:gedto bring pH eoehe value 7.40'. bu'~ :un a ootn~llt;x: SQIudon such as md(]e,u~~s not !Ii tneasUb:i; (If anything else unless the detailed

~ompos~~io.i:l of tfu.e S01U:~~Ofi is keown, in which case the mfDlm~~:iOf:l it: supplies is superfluous. The pft;:l~n~~ of CO~ in II;b~ wl'l;ill;km d'lAn~s dl~ :li~~llI:tiQn signiBI:;!I!l1:dy. ho\V~r;;~, and W~ :lIl!l!~l c()nsid~r d[rcatibl~ acudk1{ agAin in CI1:ap~~r 9,

5.13 AIDD-OIN WI!AK ACIDS .A!NDWI!AK BASI!!> AND THI!IR SA!lTS

Insread ofdissod"iluring to form lIn anio[lplus H" Ol' a Ca[nOH plus OH-, <till. LlIll.c.hllifbl'Ctd molecule canbecome an. ~.O:Ii1i. h}' binding an Hi' oran Oft .. Awell-knCfwn el{amp~e is the 1l[liliil'il1l0n.i.a molecule, NH.~, which di.ssollv'es .r.e~dily in ",rater ~nd d:'1en combines wieh H'eo fo.rm the :amj]non~lI,]:inion, Nl-]/. A s.,ibstAncr;~h!l!t binds H+ .il] rtllis'J.<'1I.CY w~lllo~r [H+]~nthe coo~u~iQn, and tlle::ttfbtt: funetions as a base .. A sulbStanc'CIIhllt hinds OH-~UIlIc:[iolls as <L1lI. 3.ddl, because .it radses [H'], It is convenient to refer to SU.cIl substances as «1ldd-on"':iLcids CJlJ[ bases ...

The quan{;b:dv~ !l!l1!1!lYlli3 o[ soludoncsconu!ining such subscaeces foUows exacdy the sarne [Jitt'OCCSS already lIpp~ie:d in thischapter, The: only mmp.liclItiO:[1 is the definirion ofcCjumlbri;u:m ccnsrants, FOJ[ 1lnadd-on. wt':aJk:1i:cid,. C, th,eequUllbri.l.'l:m .te:1i:cHo.[is ltfe

C 0111 COH

[C] [(lim]

(K "w ) i[COHI]1 1'<.;,;

(5.13.1)

thr;n the CjfU!I!ndW Rt~ bella:v~s jU$I;~i~;e K" fo~ a dissodati:ng we!llk add, The~~~r thevalue O'f [<c,. tile: sttong<:;t [jl.e <Ldd-o[l weak add, and the ]3fb!'li:;f [H+] is :~btt <L gw!:tII. [emr] and [SID]. All~he discussion of d.iss;oclJ!ti:[ig ... veak add SO~HdOIi1i properties in Sectlon 5.3 applies 00 a solution of Cpll)!.cs COH-, ~ndFi:gures 5.1, 5.2, and S.3 show the.behavior of saeh a solocioll. w]d:1 [C]il1 place of [HAll !lind! I[COI':-]] ~I] Il~!I!.ce of I[A], Por an adld~QI] weak base, tll~ ~gu~.~i~riillm reactions <Lte,

ID It1 DIH

[D~ [&1]1

KI) d.e:fiJn.ed bythis equation funericns just like Kg fOI ~. ci]soociMillig weak base iu Equarion (S.6 .. 2). This system's tm~] acid-base behavior is just like dla~ shown .. in Figures 5.6. 5.7, :and 5 . .8, with [DII ~I] P~!I!.c~ of [BOH] and [DH+] ~n ~}l!ll~e .of [B'],

[9'9)

.I\Janr ofthe weak acids and bases ]n tJ.ody fll.lJjjds are proeeins, andtheir weakprepereies are illllJnly due to tl1i~jr amino 5H~ gtl)Up5,'(l.~)~,d.lfUnction in soliI,]Jtio[las ~ddl·onba5e$. Ournodon ofa 'salt UI]!USii; be ex[~I:l,dJed by theseadd-on trl"'e<;; of ~dds and bases, 'because o:nly~hekronk fOI["lusc1I1rt become SlI.]ts. POIt example, if Hel .b :adde:.dmo a 501utflofi of 1I1rt add-on weaklaasc, D,. tothe po.i:[lJ~~haJt-IS.]DI= [[D-n.},.l[. Ji:tld. the s.o]m:ion is the.[lJe\lapcM::at:ed to dryness, cqrst:a]s of the. substance DB may be obta,illed .. Sucih "sa]ts," are usually ca]Med "ihydroo:dol'j:des'" raeherehan jU$to;;Mor~d;es. 00 enl~ll1iasize~ha~ they[egu~fr;:lbmh Hand CI.in ord;er toexist,

A s~;g:[lJif.i.C:lt[lJJtI.ow-mo]ecular~ .... veight:add-olD."I!leJik base 1:1i:I. some body Hnnds isammonea, NH~r K.c is a gas that dissolees in WilJt~ and. then combines with ll't~o form the cation NFl/ca]1ed. the al11!I1Qniil)lmkm. The name f015O;;~5 OOinl:lild:$on widl sQd~~:mal:ld pmIl5Sill,l!in~on5. b~tk is essential mrealize thalt the:y arc 5tto:ngbfl"~ w.11ie:;ttas NH", 4 is 111. weak cation.Historkal~'. N H", 4Wl'1s. supposed to be formed by dissociation of the hypotheticalweak base NH;OH formed !by the combination of N Hl wirh "\l"ilIte1".

No evidence hasbeen presented that slJ]ch a. substance c:;;:hi:[s i:rn. 1I1C]UOOR"l sd.llti,of] .. NH4~ is formed Instead by the oomb.unJitiol.n of ~:Ii:I. J-[ +- with ~. dissolved NH molecule

H

NH,1+ h therefore 1I:!li. add-om we;1I1k base, Figl]:h:s 5.6,. 5.7~ and 5.8 therefore deseribe qU1I1UnHIVdr the ac1.d-IbJist !beh:iivio:r of its golut~o!ns:;t~ constanr [NnIT~ = [NH31 + [NH/,l. fora. precise ql.lJafi{]ta~ive d.e.scr]p~ion.~hese figures .m.us~ be redrawn ~i:l1igthe ll:ppropl']ate value for K~. ~5 well as (NT\:w]1

5·.14 O'~iER:. VAhlA,iBUS

[SID] has b~~n treated ~5 if it "m;r~ the o[l~r indep~n,dJ~n~ val."~ible in ~hi5 cl1i~ptr;:r;. wr;l1iavr; assumed th:rcmghom that [1\ttU'] or [BTm1 were held cnrnst1lJm, a !lid. O:!liUy [SID~Wl'I8 allowed to. VJity. Thep-rn.cdcaJI j'l13dlic:;ttvon fo[ this tiiJeaJtn1.e[)~U3 that sig;nifilcJint changesjn [SJDI do frequend)' occur in booy fluids, bU!t: weakele'Ctro~r~econceit1trnti.ons gener:flU}' chang,e yerr~it~t]e. The I[SIfJ] value ofdtCulating pb5;l11a~5 c{.lI[ltI:cn,l!;dly ino.dJi('j~dby thr;: actnons ·of~hr;: ga$~ri)i:[llt:e',stinal tract and the; kidne;y,-, 1I1:!lid [[1>'1)' dmrtgc: sig;rnHicarnd), 0'\0"1:;[ periods of hours. The: 1[:5.1D] of ISF may be Ji]~ered IOIC:aI]yby the 8JctiOi:'ll ofi:[lJdJ;;rndual cells thaJt ma1.' "pump" NJi~ Of K~ or CI.- • .or produce ]aC'~a(e. (LaC'~Me- functions as a snong ion in botly fluidsbecaase the KA rOO.it: lac~ic $;;idis wrylarcge, on ~he QrJier of .5 N: W-~ Eq/ UterJ.

We.ak eJieICtro1yres hl.bodyHu.ids are mainly proteins, and thdr w[l;ce:nU:altl.ons, nom'l::1I.ly

vary by anallamoenrs, and very s~.ow~r, ~.cep~ in traumatic s,ir:uarions such as severe burns or heino:~rl1iage. Nonpr:orein weak el~c~:IU~~1~e5 ~.re gr;l:ler;aUy Ij["es~n~ a~ [~1i]'ll values Q[I.~hr;: order uf 'In(lM, and thdt effc::c[s o:n..lbody~fluid :add-lba5c::kl1i:.llv.~ol[ are fl~~igiMe; QO[;)TIp1l1tc:d to tl1i~J<.'>e af.c9!:tt\bon dioxide, as we sh~.I] see ~.i:'II Ch~.pter 7.]n addit:km" Jipprop.d.ate slope IC~.kul.a~io[):s sbow thll:~ equ;iyalent changes in [H'] require. twice the clian~. in [Alwr~ as in [[SID]