pKav

alues
pKaDef
ini
ti
on
pKai
sthenegat
ivebase-
10l
ogar
it
hm oft
heaci
ddi
ssoci
ati
onconst
ant(
Ka)ofasol
uti
on.

pKa=-
log10Ka

Al
so,

pKai
slogar
it
hm oft
her
eci
procal
ofdi
ssoci
ati
onconst
ant(
Ka)ofanaci
d.

pKa=l
og1/
Ka

AlowerpKav al
ueindi
cat
esast
rongeraci
d.Thati
s,t
hel
owerv
aluei
ndi
cat
est
heaci
dmor
e
f
ull
ydissoci
atesi
nwater.

Forexample,t
hepKaofacet
icaci
dis4.8,whil
ethepKaoflact
icaci
dis3.
8.Usi
ngt
hepKa
val
ues,onecanseel
act
icaci
disastrongeraci
dthanacet
icacid.

Consi
derachemi
cal
react
ion,

HA+H2O H3O++A-

Appl
yi
ngt
heLawofmassact
ion,

H3O+]
Kc=[ [A]
/[
HA]
[H2O]

Kc=Equi
l
ibr
ium Const
ant

[]=mol
arconcent
rat
ionofspeci
e

Kc[ H3O+]
H2O]=[ [A]
/[
HA]

Wher
e,Ka=Kc[
H2O]

Ka=[
H+]
[A-
]/[
HA]

Kai
scal
l
eddi
ssoci
ati
onconst
antofaci
d.

Gr
eat
ert
hev
alueofKa,
str
ongerwi
l
lbeanaci
d.

Forexample,t
heKav al
ueH3PO4i
s7.5x10-3,
whil
etheKaval
ueofHFi 5x10-4.So,
s3. the
H3PO4isst
rongeraci
dthanHFbecauseH3PO4haslar
geKaval
ue.
pKat
abl
e
 Pr
edi
cti
ngAci
d-BaseReact
ionsf
rom pKaVal
ues

ThepKav al
uesar
emostl
yusedinor
dert
hepredi
ctt
heposi
tionoftheequi
l
ibr
ium ofanacid-
basereact
ion,
aswel
lasf
orchoosi
nganaci
dorabasetoprotonat
eordeprot
onatecert
ain
speci
es.

Forexample.Thereact
ionbetweenacet
icaci
dandsodi um hy
droxi
deisasimpl
eacid-base
react
iont
haty ouhaveprobabl
yusedinyourgener
alchemistr
ycoursefort
heaci
d-basetit
rat
ion
experi
ment:

Topr
edi
ctt
heposi
ti
onoft
heequi
li
bri
um,
fol
lowt
hesest
eps:

1.I
dent
if
ytheaci
dandt
heconj
ugat
eaci
doft
hebase:

I
nt hiscase,
iti
stheacet
icaci
dandwat err
especti
vely
.Remember
,aci
dist
hepr
oton
donor(CH3COOH) ,t
hebaseisthepr
otonacceptor(–OH),
andt
heconj
ugat
eaci
disthe
protonatedf
orm oft
hebase(H2O).

2. Lookupt
hepKav
aluesoft
heaci
dandconj
ugat
eaci
d:

pKa(
CH3COOH)=4.
75,pKa(
H2O)=15.
7

3. Wr
it
ether
eact
ionequat
ionpoi
nti
ngt
heequi
l
ibr
ium posi
ti
onwi
thal
ongerar
row:

 Wat erisa1011t i
mesweakeraci d.Theref
ore,theequi
libr
ium i
sshift
edt
otheri
ght.For
suchl argedi
fferencesinacidi
ty,
thereacti
onisnotev enconsider
edasequi
l
ibr
ium and
veryof t
enacid-basereacti
onsareshownwi t
hasi ngl
earrow.
Anot
herexampl
e:Whatsi
dedoy
out
hinkt
heposi
ti
onofequi
l
ibr
ium i
sfort
hef
oll
owi
ngr
eact
ion?

Let
’sf
oll
owt
hest
epswej
ustdi
scussed.

1.I
dent
if
ytheaci
dandt
heconj
ugat
eaci
d.Theaci
dist
heal
kyne,
andt
heconj
ugat
eaci
dis
ammonia(
NH3).

2.Lookupt
hei
rpKav
alues:

pKa(
CH3CCH)=25,pKa(
NH3)=38

3. I
ndi
cat
etheposi
ti
onofequi
l
ibr
ium wi
thal
argerar
row:

Thepositi
onofequil
i
brium i
ndi
cat
esthatther
eversereact
iondoesnothappentoa
si
gnif
icantext
entandifweweretohavetheproduct
sasst ar
ti
ngmateri
al,anopposi
te
di
rect
ionarrowwouldbeneeded:

Youcanalsopredi
ctt
heacid-basereact
ionwit
houthavi
ngthepKaval
ues.Remember,
in
thebegi
nning,
wesaidthattheposi
tionofequi
li
bri
um i
salwaysont
hesideofaweaker
acidandaweakerbase.Theref
ore,
y oucancomparethebaseandt
heconjugat
ebase
i
nsteadofcompari
ngtheacidandtheconjugateaci
d.
Anot
herexampl
e:

Ther
eact
ionbet
weenphenol
andwat
er.

St
epsf
orpr
edi
cti
onofaci
dbaser
eat
ion

1.Identi
fyaci
dandconjugateaci
de.Phenol
isaci
dwhi eH+i
chdonat ontowaterand
+
becomeconj ugat
ebase,andwateri
sbaseitacceptH ionfr
om phenol
eandbeccome
conjugateaci
dinabovereact
ion.

2.Thenf
indpKav
alueoft
hesecompondf
rom pKat
abl
e.

pKa(
phenol
e)=10,pKa(
H3O)=-
1.74

3.Thephenolei
smuchweakeraci dthanH3O.Ther
efore,
theequi
li
brium i
sshiftedtot
he
l
eftsi
de.Forsuchl
argedif
fer
encesinacidi
ty,
thereact
ioni
snotev enconsideredas
equi
li
bri
um andver
yoftenaci
d-basereacti
onsareshownwithasinglearr
ow.

Anot
herexampl
e:

St
epsf
orpr
edi
cti
onofaci
dbaser
eat
ion

1.Identi
fyaci
dandconjugateaci
de.Butenei
saci
dwhi eH+i
chdonat ontoOH-andbecome
conjugat andOH-i
ebase, sbaseitacceptH+i
onfr
om but
eneandbeccomewatera
conjugateaci
dinabovereact
ion.

2.Thenf
indpKav
alueoft
hesecompondf
rom pKat
abl
e.

pKa(
ethene)=44,pKa(
H2O)=15.
7

3.TheH2Oi smuchst r
ongeracidthanbutenebecuaseithassmallerpKav al
uethan
butene.Ther
efor
e,theequil
i
br i
um i
sshiftedt
otheleftsi
de.Forsuchlargedif
ferencesi
n
acidi
ty,t
hereact
ionisnotevenconsideredasequil
i
brium andveryoft
enacid-base
reacti
onsareshownwi t
hasi ngl
earrow.
TheKeyRul
eOfAci
d-BaseReact
ions:

St
rongerAci
dPl
usASt
rongerBasePr
oducesAWeakerAci
dandAWeakerBase

Wher
edowest
artwi
tht
hispr
obl
em?

1.Remembert
hatapKat
abl
eranksmolecul
esinorderoft
hei
raci
dit
y,f
rom st
rongl
yaci
dic
(e.
g.HCl
wit
hpKaof–8)t
oweaklyaci
dic(
e.g.methane,
pKaof~50).

2.Whatdeter
mi neswhet
herornotanacid-baser
eacti
onwil
lhappenint
hefir
stpl
ace?We
appl
ythefol
lowingpri
nci
pletoaci
d-basereact
ions:
Astr
ongeracidwi
llt
endtoreact
wit
hastrongerbasetoproduceaweakeracidandaweakerbase.

3.I
t’seasyenought
ouseapKatabl
etodeter
mineaci
dstr
engt
h–wecanseeatagl ance
thatH2O(pKaof15)i
sastr
ongeraci
dthanNH3(pKaof38)
.Thequest
ioni
s,howdowe
deter
minebasestr
engt
h?

Here’
showwedoi
t.Dr
awoutt
heconj
ugat
ebasesoft
heaci
dsony
ourpkat
abl
ebyr
emov
inga
pr
oton.
E.
g.NH3–>NH2(
-)orCH4–>CH3(
-)
.

UseThe“TheWeakerTheAci
d,TheSt
rongerTheConj
ugat
eBase”Pr
inci
pleToObt
ainThe
Str
engt
hsOfBasesFrom ApKaTabl
e

Here’
st hekeypri
ncipl
e:Theorderofbasestrengthist
heinv erseofaci
dstr
engt
h.Theweaker
theacid,t
hestrongert
heconjugatebase.Usingthispr
inci
ple,y oucanal
souset
hepKatablet
o
giveyouthestr
engthsofbases.Icall
thistheinver
sepKat able.

Her
e’sapKat
abl
ewi
tht
heconj
ugat
ebasesi
ncl
uded:
ExampleA:Wehav eCH4andHO(-)WecanfindCH4ont hepKatable–ithasapKaof50.
Hydr
oxideion,HO(-
)isnotont
heleftsi
deoft
hepKatable,buti
tisonthe“i
nver
se”pKatabl
e–
i
tistheconjugat
ebaseofwater
,H2O.SoCH4i st
heacidandHO( -)i
sthebasei
nthisr
eacti
on.

Doi
ngthepr
oposedaci
dbasereact
ion,
wetransf
erapr
otonf
rom CH4t
oHO(
-)
.Thepr
oduct
s
oft
hisr
eact
ionwoul
dther
efor
ebeCH3( -
)andwater
.

Nowweaskt hequest
ion–howdot hesecompareinstr
engthtoourstar
ti
ngacidsandbases?
WaterhasapKaof~15, andCH4hasapKaof50.Ourpr oducti
sastrongeraci
d.From t
he
i
nversepKatable,
weal sonotet
hatCH3(-
)isast
rongerbasethanHO( –)
.Ourproducti
sa
st
rongerbase.

Ver
dict–thereact
ionwon’
thappen.Weneedt
ogot
oaweakeraci
d-basepai
r(see#2,
abov
e).
Sowewr i
te“NR”.

Her
e’sanot
herexampl
e.

ExampleB–TakeHCΞCHandNH2( –).HCΞCHhasapKaof25; ont heotherhand,NH2(–)i

son
theconjugatebaset
abl
e.Drawi
ngouttheproduct
softheaci
dbaser eact
ionwill
giv
eusNH3
(weakeracidthanHCΞCH)andHCΞC(–)(weakerbaset
hanNH2(–).Thisreact
ionwill
go.

ExampleC:TakeNH3andHCl.Thi
sti
me,
wecanf i
ndbothHClandNH3ont hepKatabl
e.But
HClhasapKaof(–8)andNH3hasapKaof38.HClwi
ll
clear
lyactasanaci
dhere,
andNH3wi l
l
actasabase.

Wecanwr
it
eoutouraci
dbaser
eact
ion:
HCl
+NH3→ NH4(
+)Cl
(–)

Ouracidicproduct ,NH4, hasapKaof9.Ourpr oducti

saweakeraci dthanHCl.Ourbasic
product,Cl(
-)ranksbel owNH3onouri nver
sepKascal e.Ourproducti
saweakerbaset hanNH3.
Conclusion:thisreactionisal
soago.And, indeed,ify
oufindyoursel
finafreezinghutwithonl
y
abottleofconcent ratedHCl andaqueousammoni atokeepyoucompany ,
addingthem
togetherwil
l defi
nitel
ywar m upyourday.Thisisabouttheonlysit
uati
oninwhi chIwould
recommendt his.

Deal
i
ngWi
thCompoundsThatAr
eSi
mil
ar,
ButNotOnThepKaTabl
e

Takehexane,
forinstance.Ev ent
houghitisnottechni
cal
lyontheli
st,
itsbehavi
orissi
mil
ar
enoughtomethane–t hey’r
ebothalkanes,af
teral
l–thatwemaket heassumpt i
onthatt
he
pKa’sar
eroughl
yt hesame.Si mi
l
arly,
anami neli
ketri
methyl
amine[N(CH3)3]wi
llhavesi
mil
ar
behavi
ortoNH3int her eacti
onwithHCl.
Onefi
nalpoi
ntont hebig-
picturet y
pev i
ew.Not ethepatt
ern.Theconjugat
ebaseofmet hane
(
H3C(–))isstrongenought odepr otonateanythi
ngbelowi tonthepKatabl
e( thatis,pr
etty
mucheveryt
hing).Methyl
l
ithi
um, CH3Li,i
sani ncr
edibl
ystrongbase.Conversely,acetyl
i
deion,
HCC(–)i
sstrongenought oef f
ect i
velydeprot
onateanyacidwi t
hapKaunder~25, andacetat
e
i
on(CH3COO( –))isweakerstil
l,onlyabletodeprotonat
eanyaci dwit
hapKal owert han5.

That’
swhyIcompareastrongbasel
ikemethyll
i
thi
um t
oar
oyal
flushi
npoker–i
twi
l
l
essent
ial
l
ydefeatanyhand(aci
d)i
tencount
ers.
Ref
erence

ht
tps:
//www.
mast
eror
gani
cchemi
str
y.com/
2010/
09/
29/
how-
to-
use-
a-pka-
tabl
e/

ht
tps:
//www.
chemi
str
yst
eps.
com/
det
ermi
ne-
posi
ti
on-
equi
l
ibr
ium-
aci
d-base-
react
ion/