Depar

tmentofPur
eandAppl
i
edChemi
str
y
Col
l
egeofAr
tsandSci
ences
Vi
say
asSt
ateUni
ver
sit
y
Vi
sca,
Bay
bayCi
ty,
Ley
te

EFFECTOFI
ONI
CSTRENGTHONTHEpHOFABUFFER

ASci
ent
if
icRepor
t

Submi
tt
edt
oPr
of.JacobGl
ennJansal
i
n

I
nPar
ti
alFul
fi
lment

oft
heRequi
rement
sfor

Chem 152–Phy
sical
Chemi
str
yIILabor
ator
y
 JOHNANDREB.LAO

RESHI
AMAET.DANDAN

THEORETI
CALFRAMEWORK

A.
Deby
e–Hückel
Theor
y
TheDeby e–Hückelequat ionpr ovi
desast art
ingpointformoder ntreatment sof
non- i
dealityofel ect
roly
tesol uti
ons.Int hechemi st
ryofel ect
rol
ytesoluti
ons,ani deal
soluti
oni sasol uti
onwhosecol li
gati
vepr opert
iesareproporti
onaltotheconcent r
ation
oft hesol ute.Realsolut
ionsshowdepar turesfrom t
hiskindofideali
tyatal
lbutthev er
y
l
owestconcent r
ati
ons,forexampl et heRaoul t
’sLaw.I nordertoaccommodat et hese
effectsint het hermodynami csofsol uti
ons,theconceptofact i
vit
ywasi nt
roduced:t he
propertiesar ethenpropor t
ionaltotheact i
vit
iesoftheions.Acti
vit
y,a,i
spropor t
ionalto
concent rati
on, c.Thepropor t
ionali
tyconstantisknownasanact i
vit
ycoeffi
cient,
γ.

I
nani dealel
ectr
oly
tesoluti
on,theacti
vit
ycoef fi
cientsofallt
heionsareequalto
one.Ideali
tyofelect
rol
ytesolut
ioncanbeachi evedonlyi nverydilut
esoluti
ons.Non-
i
dealit
yofmor econcentrat
edsol ut
ionsar i
sespr i
nci
pallybecausei onsofopposite
chargeat t
racteachotherduet oelectr
ostati
cf orces,whileionsoft hesamechar ge
repeleachot her.I
nconsequence,ionsar enotr andoml ydist
ri
butedt hr
oughoutthe
solut
ion,astheywouldbeinanidealsoluti
on.

Activi
tycoeff
ici
entsofsingleionscannotbemeasur edexperimental
lybecause
an electr
oly
te sol
uti
on must cont ain bot
h posi
tiv
ely charged ions and
negat
ivel
y char
gedi ons.Instead,ameanact i
vi
tycoeffi
cient
,isdefi
ned.
For example, wit
htheelectrol
yteNaCl :

I
ngener al
,themeanact
ivi
tycoef
fi
cientofaf
ull
ydi
ssoci
atedel
ect
rol
yteoff
ormul
a
AnBm i
sgiv
enby:
 Acti
v i
tycoeff
ici
ent sar et
hemselv
esfuncti
onsofconcent r
ati
onast heamountof
i
nt er-
ionicinter
acti
oni ncreasesastheconcent
rati
onoft heel
ectrol
yteincreases.Debye
andHückeldev elopedat heor
ywi t
hwhichsinglei onacti
vi
tycoef fi
cientscouldbe
calculated.Bycalculatingthemeanact i
vit
ycoeffi
cientsfr
om them thetheorycouldbe
testedagai nstexperiment aldata.I
twasfoundtogi veexcel
l
entagr eementf or"di
lut
e"
soluti
ons.

TheModel

Fi
gur
e1.Ani
deal
i
zedr
epr
esent
ati
onofasol
uti
onofa1:
1el
ect
rol
yte

A snapshotofa2- dimensi
onalsect
ionofani deal
izedel ectrolyt
esol utioni s
shownint hepict
ure.Theionsareshownasspher eswi t
huni telectricalchar ge.The
sol
vent(palebl
ue)isshownasauni for
m medium,withoutstruct
ur e.Onav erage,each
i
onissur r
oundedmor ecl
oselybyionsofopposit
echar gethanbyi onsofl ikechar ge.
Theseconceptsweredevel
opedintoaquantit
ati
vetheoryinvolvi
ngi onsofchar gez1e+
andz2e−,wherezcanbeanyi nteger.Thepr i
nci
palassumpti
onisthatdepart
urefr
om
i
deal
it
yi sduet oel ect
rost
aticinteract
ionsbetweenions,mediat
edbyCoul omb'sl
aw:
thef
orceofi nteracti
onbetweent woel ect
ri
ccharges,separ
atedbyadistance,ri
na
medi
um ofr el
ativ
eper mitt
ivi
tyεrisgivenby:

I
tisal
soassumedt
hat
:

 Thesol
utei
scompl
etel
ydi
ssoci
ated;
iti
sast
rongel
ect
rol
yte.
 I
ons ar e spher
icaland ar
e notpolar
ized byt he sur
roundi
ng el
ectr
icf i
eld.
Solv
at i
onofionsisignor
edexcepti
nsof
arasi tdeter
minestheeff
ect
ivesizesof
theions.
 Thesol
ventpl
ay snoroleotherthanpr
ovi
dingamedi
um ofconst
antr
elat
ive
per
mit
ti
vi
ty(di
elect
ri
cconst
ant).
 Ther
eisnoel
ect
rost
ri
cti
on.
 Indiv
idualionssurr
oundi
nga" central
"ioncanber epr
esent
edbyast ati
sti
cal
ly
averaged cloud ofcont
inuous charge densi
ty,wi
th a mi
nimum di
stance of
closestapproach.

Thelastassumpti
onmeanst hateachcati
onissur
roundedbyaspher i
cal
l
y
symmet
ri
ccloudofotherions.Thecloudhasanetnegati
vecharge.Si
mil
arl
yeach
ani
oni
ssurr
oundedbyacloudwithnetposi
ti
vechar
ge.

TheDeby
e-Hückel
theor
yisbasedont
hreeassumpt
ionsofhowi
onsacti
nsol
uti
on:

1.El
ect
rol
ytescompl
etel
ydi
ssoci
atei
ntoi
onsi
nsol
uti
on.
2.Sol
uti
onsofEl
ect
rol
ytesar
ever
ydi
l
ute,
ont
heor
derof0.
01M.
3.Eachi
oni
ssur
roundedbyi
onsoft
heopposi
techar
ge,
onav
erage.

Anacti
vi
tycoeff
ici
ent,γ1,
isuti
li
zedt
oconver
tfrom t
hesolut
e’smolefr
acti
on,χ1,
(asaunitofconcent
rati
on,mol efr
acti
oncanbecalcul
atedfrom ot
herconcent
rat
ion
unit
sli
kemolar
it
y,molali
ty,
orpercentbywei
ght
)toacti
vi
ty,ɑ1.
 TheDeby
e–Hückelli
mit
ingl
awenabl
esonetodeter
minetheact
ivi
tycoef
fi
cient
ofani
oni
nadil
utesol
uti
onofknowni
onicst
rengt
h.Theequat
ioni
sgivenby:

wher
e,

 εi sthediel
ectr
icconstant
,
 z+ and 
z− 
arethechargesofthecat
ionandanion,r
espect
ivel
y,
 I 
isaquant i
tycall
edtheioni
cstr
engthofthesolut
ion,
and
 Ti sthetemperatur
eoft heel
ect
rol
ytesol
uti
on.

B.pHmet
er

ApHmet eri
sapot enti
omet erusedtomeasuret heH+concentrat
ioninsoluti
on.
Anel ect
ri
cpotenti
ali
smeasur edt hatdependsont hev olt
agediff
erencebetweena
refer
enceelect
rode,usuall
ycal omel,andagl assel ectr
odet hatissensit
ivet o H+
+
concentr
ati
on.Theglassmembr aneact sasifiti
ssel ecti
velyper
meabl etoH whi l
e
othercati
onsandanionsar eexcluded.Thispermeabili
tyresult
sinapot ent
ialacross
themembr anet
hatisalinearf
unctionofthepH.

Basi
cally
,threepar ametersareinvol
vedi nthemeasur ement :theactualmolar
concentrat
ion ofhy drogen ions,the di
ssociati
on const
antoft he acid( pKa)
,and
temperatur
e.pH i sdef i
nedast henegativ
eoft helogari
thm tot hebase10oft he
+
hydrogenionconcent rati
on( pH =–log10[H] ).Thehy dr
ogenel ectr
odewast hefi
rst
elect
rodetobeusedf orpHmeasur ementbuti tr
equir
edasuppl yofhy drogengasand
thusit
sappl i
cati
onwasl imited.
 Fi
gur
e2.Oper
ati
onal
Def
ini
ti
onofpH

Thest arti
ngpoi ntisanel ect rochemi calcel l.Thecel lconsi stsofani ndicat i
ng
electr
odewhosepot entialisdi r
ectlypr opor ti
onalt opH,ar ef erenceel ectrodewhose
potentialisindependentofpH, andt hel iquidt obemeasur ed.Theov erallvoltageoft he
celldependsont hepH oft hesampl e.Becausedi f
ferenti ndi cati
ngel ectrodeshav e
sli
ghtlydifferentresponsest opH, themeasur i
ngsy stem mustbecal i
brat edbef oreuse.
Thesecond st ep i nt heoper ati
onaldef initi
on ofpH i scal ibrati
on.Thesy stem i s
cali
bratedbypl aci
ngt heel ectr
odesi nsol utionsofknownpHandmeasur ingt hev oltage
oft hecel l
.Cel lvol t
agei sal inearf unct ionofpH,soonl yt wocal i
brat i
onpoi ntsar e
needed.Thef inalst epi nt heoper at i
onaldef init
ioni st opl acet heel ectrodesi nt he
sampl e,measur et hev olt
age,anddet ermi net hepH f rom t hecal i
brat i
ondat a.I tis
apparentt hatt hepr act i
caldet erminat ionofpHr equiresst andar dsolutionsofknown
pH.Thest andardsol utionsar ecal l
edbuf fers,andt hepH v al
uesassi gnedt ot hem
definet hepHscal e.Det erminingpHv aluesr equi resmaki ngassumpt ionsconcer ning
the chemi caland phy sicalpr oper ti
es of el ectroly
t e sol ut i
ons.Sl ightl
y di fferent
assumpt i
onsl eadt o slightlydi ff
er entpH v aluesf ort hesamesol ut i
on.Ther ef ore,
sli
ghtlydifferentpHscal escanexi st.

Bef oreapHmet erisused, theelect r

odesmustber insedwi thdisti
lledwat erand
all
owed t o drain.Theycan bebl ott
ed wi th a papert issue.Themet ershoul d be
standardizedwi t
ht wobuf fers,onewi t
hpHbel owandonewi thpHabov et hev al
uest o
bemeasur ed.Thet emperatur eoft hest andardbuf f
ersshoul dbemeasur edandt he
temper aturecompensat ioncont r oladjustedt othet emper at ureoft hesol ution.When
themet erhasbeenst andardizedandr eadingsar est abl e,t hepHoft het estsol ut
ion
can be measur ed.Met er
s wi t
ht wo separ ate el ectrodes,t he glass and cal omel
electr
odes,ar eusedi fthev olumeofsol uti
oni sadequat e.Acombi nati
onel ectrode,in
whichbot ht her efer
enceel ectrodeandt heglassel ectrodear eincorporatedi ntoone
sli
mt ubei susef ulforverysmal lvolumes.Er rorsinpHmeasur ementmayar iseint he
presenceofhi ghNa+concent rat i
on,athi ghi onicst rengt hsuchaswi thammoni um
sulfat
esol utions, andwithelectrodesf ouledbypr oteinsorot herbiopolymer s.Af t
eruse,
electr
odesshoul dber i
nsedwi thwat erandst oredaccor dingtot hemanuf acturer'
s
di
rect
ions(
typi
cal
l
yimmer
sedi
nst
oragebuf
fer
stoav
oiddr
ying)
.
I
NTRODUCTI
ON

Vir
tually al lbi ochemi calexper iments are car r
ied outin aqueous sol uti
ons
cont aini
ngspeci ficsal tsthathel pmi ni mizechangesi nt hepH oft hesol utionupon
+ -
addi t
ionofasmal lamountofaci d(H )orbase( OH) .Thesesalt s,whendi ssolvedin
solution,arer eferredt oasbuf fers.Theyconsi stofaweakaci dspeci es(thepr otonated
form,HA)t hati sr esponsi blef orconsumpt i
onofaddedbase,andi tsconj ugatebase
+
(thedepr otonat edf orm,A)t hatconsumesaddedaci dorH .Thecont rolofpH i s
i
mpor tantinor gani smsandt hei rcell
sbecausechemi calreact
ionsandpr ocessesar e
affectedbyt hehy dr ogeni onconcent ration.Buf
fersar ecomposedofmi xturesofweak
acidsandt hei rcor r espondi ngsal t
s.Usi ngtheBr onsted-Lowrydef i
niti
on,anaci disa
compoundt hatcandonat eahy drogeni on.Aweakaci disonethatdoesnotcompl etel
y
i
oni ze,ordissoci ate,i nsol uti
on.Theext entofdissociationisgivenbyt heequi l
ibri
um
const antKaf ort her eacti
on:
HA↔ H++A–

Theequil
ibr
ium const
antfortheioni
zati
onofthi
sacidisthen:Ka=[H+]
[A–]
/[
HA].
Thi
sisthemeasur eoftheeasewi t
hwhi chtheaci
ddonatesitshy dr
ogenion.Higher
Ka’
sindi
cat
et hattheacidwilldi
ssociatemorecompletel
yintoions.TheHenderson-
Hassel
bal
chequation:

pH=pKa+l
og[
A]/
[HA]

permitst hecalcul ati

onoft hepHf rom t her ati
ooft hesalttotheaci d.IfH+isaddedt o
suchasol uti
on, theacidconcent r
ationi ncreaseswhi l
ethesaltconcent rat
iondecreases
andt hepHi sl ower ed.Conv ersely,ifOH– i sadded,t hesaltconcent rat
ionincreases
whiletheaci dconcent rati
ondecr easesandt hepH oft hebuf fermi xt
ureisr ai
sed.
Hydrogeni onconcent rationisusual lymeasur edwi thapHmet er
, aglasselectr
odeand
ar eference el ect r
ode.The pH met eri s a pot entiometer,capabl e ofaccur atel
y
measur ingsmal lelectr
icalpot ent
ialdi ff
erences.Thegl asselectrodeconsi st
sofat hin
bubbleofsof tglasst hatcont ainsasol uti
onofKClandacet icacidi nwhichapl ati
num
wireisimmer sed.Anel ectri
calpot entialisdev elopedacr ossthegl assbubble,whichis
proport
ional tohy dr
ogeni onconcent rati
on.

I
naddit
iontoaf
fect
ingthepHofasol uti
on,buff
ersalsoaff
ecttheionicst
rength
ofasol
uti
onbecausebuff
ersareoftenionicspeci
es,whichhaveelectr
ostati
cchar ge.
Thei
onicst
rengt
hofasoluti
oncontaini
ngioni
cspeciestakesint
oaccountt wofactors:
theconcent
rati
onofallthei
onsi
nsol
uti
onandt
hechar
gesquar
edofeachspeci
es,
accor
dingtotheequat
ion:

wherecii st heconcent r
ationofeachi onicspeciesandZi2 i st hechar gesquaredf or
eachi oni
cspeci es.Considerati
onofi onicst r
ength( I
)isv eryi
mpor tantforanumberof
reasons.Wat ersol
ublepr otei
nsar echar gedspeci est hatint
eractwi t
hot herproteins,
smal lchargedmol eculesf r
eei nsolution,orsmal lmol eculesfixedonasol i
dsur face
(such as wi thi on exchange resins).These i nt
er actions,which are Coulombi c or
elect
r ost
ati
ci nnature,arest r
onglyinfluencedbyt hei oni cstr
engthoft hesolution.I n
this experi
ment ,the phosphat e buffersol ut
ion wi l
lbe pr epared byt he conjugat e
acid/basepai ratpHof9( desiredpH)i nor dertocalculateitsi
onicst r
ength.

Na2HPO4+NaOH→ HPO42-+PO43-

Obj
ect
ives

Thi
sexper
imentai
mst
o:

 pr
epar
eabuf
fersol
uti
onatagi
venpHandconcent
rat
ion;
 cal
cul
atet
hei
oni
cst
rengt
hoft
hebuf
fersol
uti
on;
 v
aryt
hei
oni
cst
rengt
hoft
hebuf
ferbyaddi
ngNaCl
;and
 plott
heactivi
tycoef
fi
cientandt
hei
oni
cst
rengt
hoft
hebuf
fersol
uti
ont
oshow
thei
rrel
ati
onship.
 MATERI
ALSANDMETHODS

Appar
atus:

1Lv ol
umetr
icf
lask,
beaker(
100mL)
,pHmet
er,
hotpl
ate,
sti
rr
ingr
od,
alumi
num
f
oil
,spat
ula,medi
ci
nedropper
.

Chemi
cal
s:
 0.
05M Na2HPO4,
0.1M NaOH,
0.1M H3PO4,
anddi
sti
l
ledwat
er

Exper
iment
alPr
ocedur
e:

A.Cal
i
brat
ionoft
hepHmet
er

1.All
ow allofthebuf f
erst or eacht hesamet emper atur
e,sincepH readingsare
temperat
uredependant.Ifthebuf fersarenotat25° C, t
emperatur
ecompensat i
onis
recommended.Measur et het emper at
ureoft hebuf f
ersusingaNI ST traceabl
e
thermometerandmanual l
yent erthet emperatur
ei ntothemet eroruseanATC
probetoautomati
cal
lytransmi tthetemper at
ureofthebuf fer
st ot
hemet er
.

2.PreparethepH10.01buffer,pH7.00buff
erandpH4.
01buff
erasdescribedi
nthe
Cali
brati
onBuf
ferPrepar
ationsect
ionanduncov
ert
hecal
i
brat
ionbeaker
s.

3.RinsethepH el
ectr
odef i
rstwithdeionizedwat erandtheninthepH 10.
01buf
fer
ri
nsebeaker.Makesur etorinsetheel ectr
odewi t
hdeioni
zedwateroverawaste
beakertopreventcontaminati
onoft hebuf f
ers.Theelectr
odeshouldnev
erbe
ri
nsedinthesamebufferbeakerthatwillbeusedforcal
i
brati
on.

4.Placetheel ect
rodei
ntot
hepH10.01buff
ercali
brat
ionbeaker
,sotheel
ect
rodet
ip
andj unct
ionar eful
l
yimmersedi
nt hebuff
er,andstirt
hebuf f
eratamoderat
e,
unifor
mr ate.

5.St
artt
hecal
i
brat
ionont
hemet
er.

6.Waitforast abl
er eadinginthepH 10.01buffer,atleast1t o2mi nutes.Ift
he
temperat
ureofthebufferwasenter
edmanual l
yoranATCpr obeisi nuse,themeter
shoul
daut omati
call
yrecogniz
ethebufferanddisplayit
st emper ature-
corr
ectedpH
val
ue.Ift
hemet erdoesnotautomati
cal
lyrecogni
zet hebuffer,enterthevalueoft
he
pHbufferatit
smeasur edtemper
atur
e.

7.Oncethecorr
ectbuf
ferv
aluei
sent
ered,pr
omptt
hemet
ert
opr
oceedt
othenext
cal
ibr
ati
onpoi
nt.

8.RinsethepHel ectr
odef i
rstwithdeionizedwaterandtheninthepH7.00buff
erri
nse
beaker.Makesur etorinsetheelectrodewit
hdei oni
zedwateroverawast
ebeakerto
preventcontaminati
onoft hebuffers.Theelectrodeshoul
dnev erberi
nsedinthe
samebuf ferbeakerthatwillbeusedf orcal
ibr
ati
on.

9.Pl
acet
heel
ect
rodei
ntot
hepH7.
00buf
fercal
i
brat
ionbeaker
,sot
heel
ect
rodet
ip
 andjunct
ionaref
ull
yimmer
sedi
nthebuf
fer
,andst
irt
hebuf
feratamoder
ate,
uni
for
mr ate.

10.
Waitforast ablereadinginthepH 7.00buffer,atleast1t o2mi nutes.Ift
he
temperat
ureofthebufferwasenter
edmanuall
yoranATCpr obeisi nuse,themeter
shoul
daut omati
call
yrecogniz
ethebuff
eranddi spl
ayitstemper ature-
corr
ectedpH
val
ue.I
fthemet erdoesnotautomati
cal
l
yrecognizethebuffer,enterthevalueoft
he
pHbufferatit
smeasur edtemper
atur
e.

11.
Oncethecorr
ectbuf
ferv
aluei
sent
ered,pr
omptt
hemet
ert
opr
oceedt
othenext
cal
ibr
ati
onpoi
nt.

12.
RinsethepHel ectr
odef i
rstwithdeionizedwaterandtheninthepH4.01buff
erri
nse
beaker.Makesur etorinsetheelectrodewit
hdei oni
zedwateroverawast
ebeakerto
preventcontaminati
onoft hebuffers.Theelectrodeshoul
dnev erberi
nsedinthe
samebuf ferbeakerthatwillbeusedf orcal
ibr
ati
on.

13.
Placetheel ect
rodei
ntot
hepH4.
01buf
fercal
ibr
ati
onbeaker
,sotheel
ect
rodet
ip
andj unct
ionar eful
l
yimmer
sedi
nthebuff
er,andsti
rthebuff
eratamoderat
e,
unifor
mr ate.

14.
Waitforast ablereadinginthepH 4.01buffer,atleast1t o2mi nutes.Ift
he
temperat
ureofthebufferwasenter
edmanuall
yoranATCpr obeisi nuse,themeter
shoul
daut omati
call
yrecogniz
ethebuff
eranddi spl
ayitstemper ature-
corr
ectedpH
val
ue.I
fthemet erdoesnotautomati
cal
l
yrecognizethebuffer,enterthevalueoft
he
pHbufferatit
smeasur edtemper
atur
e.

15.
Oncethecorr
ectbuf
ferv
aluei
sent
ered,pr
omptt
hemet
ert
osav
eandendt
he
cal
ibr
ati
on.

16.
RinsethepHelectr
odewithdei
onizedwaterandstor
etheel
ectr
odeinpHelect
rode
storagesol
uti
on.Covert
hecali
brat
ionbeaker
swithawatchgl
assorpar
afi
l
m.

B.Pr
epar
ati
onoft
hephosphat
ebuf
fer

1.1Lof0.05M disodi
um hy
drogenphosphat
esolut
ionwi
l
lbepr
epar
edbydi
ssol
vi
ng
Na2HPO4(
7.098g,50mmol)ofi
n1Lofdisti
l
ledwater
.
2.25mLofasol
uti
onof0.
05M Na2HPO4wi
l
lbest
ir
redat30º
C.
3.DecideonthepHf oryourbuf
fer.Thi
spHshoul
dbewithi
nonepHunitfrom thepKa
oftheaci
d/conj
ugatebase.So,onecanpr
epar
eabuff
eratpH2orpH7, forexample,
butpH9woul dbepushi ngit
.CheckthepHusingapHmeterandadjustthepHas
 necessar
yusingphosphor
icaci
dorsodi
um hy
droxi
de.ThepHwi
l
lbeadj
ust
edt
othe
requi
redval
uebyadding0.
1M NaOH.
4.Measur
et heioni
cst
rengt
hoft hepr
eparedbuf
ferwit
ht hechosenpH.Cal
cul
atet
he
i
oni
cstrengthusi
ngt
heextendedDebye-
Huckelequat
ion.

5.Graphtheresultusi
ngslope-
int
erceptfor
m oftheli
ney=mx+bt akingtheaccountof
theioni
cstrengthofthebuff
er(x-
axis)andact
ivi
tycoef
fi
cient(
y-axi
s),
anddetermine
thei
rrel
ati
onship.
6.Uset heHender son-Hassel
bachequationt
o cal
cul
atehow muchacidandbase
needed.Theequat i
oncanbesi mpli
fytomake1li
terofbuf
fer
.Sel
ectt
hepKaval
ue
thati
sclosestt
ot hepHofy ourbuf
fer.
pH-
pKa=l
og[
A]/
[HA]

RESULTSANDDI
SCUSSI
ON

Abuf ferisanaqueoussol uti

onconsi
sti
ngofami xtureofaweakaci dandi ts
conjugatebaseoraweakbaseandi tsconj
ugateaci
d.Abuf fer’
spHchangesv eryl
i
ttle
whenasmal lamountofst r
ongaci dorbaseisaddedt oit.Itistherefor
eusedt o
preventchangei nthepHofasol uti
onuponaddit
ionofanotheracidorbase.Meanwhi le,
i
onicst r
engthofasol uti
onisaf uncti
onoftheconcentrat
ionofal lionspresenti
na
soluti
on.
Intheexper iment,t
hebuf f
erthatwasusedwast hedi basicphosphatebuffer
whichispr eparedbydi l
uti
ng7.10gK2HPO4 in1Ldi st
il
ledwat er.Phosphori
cacidisa
tr
iproti
cacidwhi chundergoesastepwisedi
ssoci
ati
onasf ol
lows,

wher
eK1  5x10-3 
=6. ;K2  2x10-8 
=6. ;andK3  6x10-13.Eachoft
=3. heset
hree
equi
l
ibr
ium equat
ionscanbeexpr
essedmathemat
ical
l
yinsever
aldi
ff
erentway
s.
Taki
ngtheequati
onforK2 
asanexample,
eachoft
hefoll
owingi
sequival
ent
:

wherepH=- l H+ 
og[ ]
,andpK2 =-l  
ogK2.Thebuff
ersolut
ionhaspHof9. 96i
nallthr
ee
t
ri
alsshowninTabl
e1atr oom t
emperatur
e.Thecalcul
atedi
oni
cstrengt
hwas0.2.pH
meterusedwasf
ir
stcali
brat
edbefor
emeasuringthepHofasolut
ion.

Tabl
e1.I
nit
ial
readi
ngoft
hephosphat
ebuf
fer

Tr
ial
s pH
1 9.
96at29.
7°C
2 9.
96at29.
7°C
3 9.
96at29.
6°C

Thedesi
redpH oft
hebuf
ferf
ort
heexper
imenti
s9.I
nor
dert
oachi
evet
he
desi
redpH,
dropsof0.
1M H3PO4wasaddedi
nthesol
uti
on.H3PO4i
susedt
oadj
ustt
he
pH si
nce i
tis a weak aci
d hav
ing weak di
ssoci
ati
on const
antand due t
othi
s,
phosphor
icaci
ddoesnotr
eactwi
tht
henor
mall
ogar
it
hmi
cresponseasast
rongaci
d
andt
endst
obuf
ferneut
ral
i
zat
ionr
eact
ions.Thi
smakesf
orasl
owerr
eact
iont
hati
s
easi
ert
ocont
rol
.Showni
nTabl
e2t
henumberofdr
opsofH3PO4addedt
oeachoft
he
t
ri
als.I
tcanbeobser
vedt
hatpH9wasachi
evedaf
ter5dr
opsof0.
1M H3PO4f
oral
lthe
t
ri
als.Thei
oni
cst
rengt
hobt
ainedaf
teraddi
ngH3PO4was0.
61.

Tabl
e2.Readi
ngsofpHaf
tert
headdi
ti
onofH3PO4

Numberofdr
ops Fi
rstt
ri
al Secondt
ri
al Thi
rdt
ri
al
1dr
op 9.
62at29.
7°C 9.
63at29.
6°C 9.
54at29.
7°C
 2dr
ops 9.
38at29.
5°C 9.
54at29.
7°C 9.
36at29.
8°C
3dr
ops 9.
30at29.
6°C 9.
25at29.
8°C 9.
20at29.
9°C
4dr
ops 9.
12at29.
7°C 9.
04at29.
8°C 9.
09at29.
9°C
5dr
ops 9.
00at29.
7°C 9.
00at29.
8°C 9.
00at29.
8°C

Buf
ferr
esi
stt
ochangei
npH howev
er,adj
ust
ingi
tsi
oni
cst
rengt
hthr
ought
he
addi
ti
onofsal
tsmayaf
fecti
tspH.Addi
ti
onofneut
ralsal
tssuchassodi
um chl
ori
de
af
fectpHofabuf
fersol
uti
onbyal
ter
ingi
oni
cst
rengt
h.I
oni
cst
rengt
haf
fect
sioni
zat
ion
const
ant
s,act
ivi
tyofi
oni
zedspeci
es(
sal
tfor
m)oft
hebuf
fer
,andact
ivi
tyofhy
droni
um
i
onwhi
chal
ter
spHofsol
uti
on.Ont
heot
herhand,
addi
ti
onofwat
er(
dil
uti
on)t
oabuf
fer
sol
uti
oncanal
teri
tspHduet
oreduct
ioni
nioni
cst
rengt
h.Thef
oll
owi
ngbuf
ferequat
ion
f
oran aci
d(HA)and i
ts conj
ugat A-)account
e base ( sfort
he i
oni
c st
rengt
h by
i
ncor
por
ati
ngact
ivi
tycoef
fi
cientt
erm,
γA- 
:

pH=0.
53+

act
ivi
tycoef
fi
ci
ent
 i
susual
l
ylesst
han1.Accor
dingl
y,l
ogγA- 
i
snegat
ive.Thus,i
tis
expect
ed t
o hav
elowerpH f
oraci
d-conj
ugat
e base pai
rwhen i
oni
c st
rengt
his
account
edf
or.I
tcanbeobser
vedi
nthev
aluesshowni
n Tabl
e3.t
hatt
hepHoft
he
sol
uti
onhasdecl
i
ned.Thecal
cul
atedpHusi
ngt
heequat
ionabov
ewas3.
00whi
l
ethe
pH obt
ainedbef
oreaddi
ngNaClwas7.
64.Thi
ssi
gni
fyt
hatt
hepH oft
hebuf
feri
s
changedast
hei
oni
cst
rengt
hoft
hesol
uti
oni
svar
ied.

Tabl
e3.Readi
ngsofpHaf
tert
headdi
ti
onofNaCl

Numberofdr
ops Fi
rstt
ri
al Secondt
ri
al Thi
rdt
ri
al
1dr
op 7.
01at26.
4°C 6.
96at26.
9°C 6.
99at26.
2°C
2dr
ops 7.
01at26.
5°C 6.
96at27.
3°C 7.
00at26.
2°C
3dr
ops 7.
01at26.
7°C 6.
96at27.
3°C 7.
00at26.
5°C
 Fi
gur
e1.pHv
s.meani
oni
cact
ivi
ty

Thegr aphshowst hattherei

sani nver
ser el
ationshi
pbet weent hechangei n
i
onicstrengthandpH.Fr om t
hecomputedpHof7. 64,itdecreasestoapHof3.Thi sis
againduet ot headdit
ionofsal twhi
chistheNaClsincei talt
ersandr educetheionic
str
engthi nwhi cht
hei oni
cst r
engthaf
fectsioni
zati
onconst ant
s,activ
ityofionized
species(sal
tf orm)oft hebuffer
,andactiv
ityofhy dronium ionwhichal t
erspH of
sol
ution.
Concl
usi
on
Itcanbeconcludedthattherei
sani nverserelati
onshipbetweenpHandi oni
c
strength.Thecomputedmeani onicacti
vit
ywer e0.44and0. 54witht
hepH3and7. 64
respectivel
y.Thedecr
easeinpHi sduet othesaltwhi chistheNaCl t
hatalt
ersand
reducet heioni
cstr
engthwhichsignif
iestheionizat
ionconst antandtheacti
vi
tyofthe
i
oni zedspeciesinasol
uti
on.

Ref
erences

https:
//www. emedicalprep.com/study
-mat
eri
al/
chemi
str
y/i
oni
c-equi
l
li
bri
um/
arr
heni
us-
theory-
of-
electr
oly
tic-dissociat
ion/

ht
tps:
//www. aski
it
ians.com/ii
t-
jee-
chemi
str
y/phy
sical
-chemi
str
y/ar
rheni
us-
theor
y-of
-
el
ectr
olyt
ic-
dissoci
ation.aspx

htt
ps:
//chem.l
ibr
etext
s.org/
Text
book_
Maps/Physi
cal
_and_Theor
eti
cal
_Chemi
str
y_Text
book_Maps/Map%3A_ Physi
cal
_Chemi
str
y_f
or_
the_Bi
osci
ences_(
Chang)/
05%3A_Sol
uti
o
ns/5.
08%3A_Ioni
c_Acti
vit
y

ht
tps:
//chem.l
ibr
etext
s.org/
Core/Physi
cal
_and_Theoret
ical
_Chemist
ry/
Phy
sical
_Pr
oper
t
i
es_of
_Mat t
er/
Soluti
ons_and_Mixt
ures/
Nonideal
_Soluti
ons/Deby
e-H%C3%BCckel
Chang,Raymond.Physi
calchemist
ryfort
hechemical
andbi
ologi
cal
sci
ences.3r
ded.
Sausal
i
to,Cal
if
:Univer
sit
yScienceBooks,2000.
Ochi
ai,
E-I
.(1990)"
Par
adoxoft
heAct
ivi
tyCoef
fi
cientγ±.
"J.Chem.Educ.67:
489.

Howsal
tconcent
rat
ional
tert
hepHofabuf
fer
?
Thisint
eract
ioncanbeexpl ainedbyt heef f
ectofi ncreasingthesaltconcent
rat
ionont hepH of
aqueoussoluti
ons.Inplainwor ds,byraisingtheionicstrengthofanaqueoussoluti
on,basedonthe
Debye–Huckelequat ion,theactiv
ityoft hehy dr
oxideiondecr eases.I
notherwords,byaddingsal
t
toanaqueoussol ut
ionwi thahi ghorl ow pH duet oi ncreasi
ngtheioni
cst r
ength,t
hepH drif
ts
towardsthecenterofthepHspect rum ( pH=7) "

APPENDI
X
Di
ssoci
ati
on
K2HPO4+2H2O 2KOH+H3PO4
aci
d base conj
.aci
dconj
.base
3K2HPO4+H3PO4 2HPO42-+2H2PO4-+6K+
base aci
d conj
.aci
d conj
.base
HPO42-+OH-PO43-+H2O
HPO42-+Cl
-
 PO43-+HCl
aci
d baseconj
.aci
dconj
.base
Sol
vi
ngf
ormol
ali
ty
7.
10g0.
05M K2HPO4(
mol
/L) mol
/kg=m
 3molK2HPO4
7.
10gK2HPO4 X =0.
04mol
K2HPO4
174.
17g
K2=39.
10(
2)=78.
2g
H=1.
00=1.
00g
P=30.
97=30.
97g
O4=16.
00(
4)=64.
00g
174.
17g
1000mL 1g 1kg
1LH2OX x x =1kg
1L 1mL 1000g
mol solut
e 0.04molK2HPO4
Ther
efor
e,mol
ali
ty= = =0.
44m
kgsolute 1kgH2O
K2HPO4 i
nwat
eri
oni
cst
rengt
handmeani
oni
cact
ivi
ty
2 2
I=½[
(0.
04m)
(+1)+(
0.04m)
(-
2) ]
I=0.
2
A|2+2-
|I 1. 2|0.
171m | 2
ogy
l ±=- =- =-
0.61
1+B I 6m 0.
1+1. 2
±=e-0.61=0.
y 54
K2HPO4i
ntheaddi
ti
onH3PO4i
oni
cst
rengt
handmeani
oni
cact
ivi
ty
3molK2HPO4
7.
10gK2HPO4X =0.
122mol
K2HPO4
174.
17gK2HPO4
2 2
ogy
l ±=I=½[
2(0.
122)
(+1)+(
0.122)
(-
2) ]=0.
61
1.
171m |
2|0.61
ogy
l ±=- =-
0.81
1+1.
6m 0.61
y
±=0.
44
K2HPO4i
ntheaddi
ti
onofNaCl
ioni
cst
rengt
handmeani
oni
cact
ivi
ty

3molK2HPO4
7.
10gK2HPO4X =0.
04mol
K2HPO4
174.
17g
 NaCl
sol
vent
mol 1L
0.
1 x 0.
1m
L 1kg

2 2
I=½[
2(0.
1m)
(+1)+(
0.1m)
(-
2) ]=0.
5
1.
171m |
2|0.
5
ogy
l ±=- =-
0.77
1+1.
6m 0.5
y
±=0.
46

Cal
cul
ati
onofpHf
orH3PO4
pka=-
log(
6.3x10-8)=7.
20

ph=7.
20+l
og(
1)+0.
444=7.
64
Cal
cul
ati
onofpHf
orNaCl
pka=-
logKa(
H3PO4)
=-
log(
7.1x10-3)=2.
15

0.
5
2.2.
15+l
og( )+0.
44=3.
00
0.
1