Acids and bases.

[HA][OH− ]
pH computations. Kb ' (8)
[A− ]
Axel Hunding Kb is the ionization constant for the base.
Note that the reaction (7) is not the reverse
of (3) and thus Kb is not the reciprocal of
Ka . Rather we get

A (Brønsted-) acid is a species, which do-

nates a proton (H+ ) to another species: [H3 O+ ][A− ] [HA][OH− ]
Ka Kb =
[HA] [A− ]
HA + B
A− + HB (1) = [H3 O+ ][OH− ] = Kw (9)
The proton acceptor is called a base. Thus
in general (Concentration-) pH is defined as
pH = − log[H3 O+ ].
With similar notations, we get
Acid1 + Base2
Base1 + Acid2 (2)

When HA looses a proton, the generated pH + pOH = pK w = 14.0 (10)

species (here A− ) is called the corresponding pKa + pKb = pKw = 14.0 (11)
(or conjugate) base to HA.
Usually the solvent is water, and an acid Some acids are practically completely dis-
may react with water according to sociated in water, and are known as strong
acids. Examples are HCl, HNO3 and HClO4 .
If such an acid is dissolved in water with the
HA + H2 O
A− + H3 O+ (3) nominal concentration C, the actual con-

The corresponding equilibrium constant centration of the acid is very small, and
pH = − log[H3 O+ ] ' − log C. Thus a very
diluted solution of hydrochloric acid with
[H3 O+ ][A− ] [H3 O+ ][A− ]
(4) C = 1.0 10 M has pH = 3.0. Correspond-
−3
Ka = '
[HA]xH2 O [HA] ingly, a 0.1 M solution of sodium hydroxide
has pOH = 1.0, and thus a pH = 14.0 - 1.0
is called the ionization constant of the acid.
= 13.0.
For the auto-ionization of water
If solutions of HCl and NaOH are mixed,
H3 O+ and OH− react to water, and a sur-
H2 O + H2 O
OH− + H3 O+ (5) plus of one of the ions thus defines the pH:
20.0 mL of 0.200 M HCl and 15.0 mL 0.100
we have the equilibrium constant M NaOH yields (approximately) 35.0 mL
solution. There is 20.0 × 0.200 = 4.00mmol
+
Kw ' [H3 O ][OH ] −
(6) of HCl and 1.50 mmol of NaOH initially, but
after reaction only 4.00 - 1.5 = 2.50 mmol
where we have omitted the possible devia-
H3 O+ left. The result is thus a solution of a
tion from one of xH2 O . Kw has the value
strong acid for which pH is easily estimated:
1.0 10−14 M2 at 25o C.
pH = − log(2.50/35.0) = 1.15.
For the base A− we also have the equilib-
rium If the acid does not dissociate completely, it
is called a weak acid. This happens, when
Ka  1.
A− + H2 O
HA + OH− (7) Analogously, a weak base has Kb  1.

with the equilibrium constant

1
pH in weak acid p
If a nominal concentration of HA is given x= Kb C (16)
as C, HA dissociates and leaves an actual
concentration C-x As above this may be rewritten
HA + H2 O
A− + H3 O+
(I) C - -
(II) C-x x x pKb + pC
Here we have neglegted the contribution from pOH = (17)
2
the auto-ionization of water to [H3 O+ ]. We
get

x2
Ka = (12) For a 0.1 M solution of sodium acetate, we
C−x thus have
which may be solved for x, in terms of C
and Ka . Quite often x  C and x may then
be neglected in the denominator, with the 14.0 − 4.75 + 1.0
pOH = = 5.125 (18)
approximate result 2
p and again x  C.
x = Ka C (13) For pH we get 14.0 - 5.125 = 8.88.
which may be rewritten pH in a buffer (weak acid plus corre-
sponding weak base)
If both HAc and its corresponding base Ac−
pKa + pC are added, we get
pH = (14)
2 HA + H2 O
A− + H 3 O+
Ca Cb -
Thus for a 0.1 M solution of acetic acid HAc Ca − x Cb + x x
(pKa = 4.75) we get pH = (4.75 + 1.0)/2 = and inserted in K a this yields
2.88. (Cb + x)x Cb
Ka = 'x (19)
We check this result: Ca − x Ca
x = 10−2.88 = 1.33 10−3  C and thus our where we assume that x = [H O+ ] is much
3
approximation is validated. For the degree smaller than both C and C . We thus get
a b
α of dissociation we get α = x/C = 0.0133
and thus only about one per cent of the x = Ka Ca /Cb (20)
weak acid is dissociated.
which may be rewritten
pH in weak base
The corresponding base to acetic acid is the
acetate ion Ac− . For the reaction with wa-
Cb
ter, we have pH = pKa + log (21)
Ca
Ac−
+ H2 O
HAc + OH −

(I) C - -
(II) C-x x x which is known as the buffer equation. For
We get a solution which has nominal concentrations
C(HAc) = 0.100 M and C(Ac− ) = 0.200 M
x2 x2 we get
Kb = ' (15)
C−x C
with x = [OH ] and thus
−
0.200
pH = 4.75 + log = 5.05 (22)
0.100

2
Thus x  Ca < Cb is fulfilled. Here we have tacitly used the rule
pH in weak acid plus strong acid ‘The strongest acid reacts with the strongest
base, until one is depleted’. Initially there
If we mix HCl with HAc, we get are two acids, NH+ 4 and H2 O, of which the
+
HA + H 2 O
A− + H 3 O+ (weak) acid NH4 is the strongest. Simi-
Ca - CH larly, OH− is a stronger base than water.
Ca − x x CH + x We thus let NH+ 4 and OH react until one
−

and inserted in Ka this yields is depleted. The content of the solution is

then examined, and we observe that it is
x(CH + x) xCH composed of a mixture, for which we can
Ka = ' (23)
Ca − x Ca fairly easily estimate pH.
Note that [H3 O+ ] = CH + x now. We may Also the strong base was present in an
estimate x as amount less than that of the weak acid. If
OH− had been in excess, we had been left
x = Ka Ca /CH (24) with a mixture of a weak base (NH3 ) and the
As an example consider Ca = 0.100 M and excess of OH− . Again, this is a situation we
C(HCl) ≡ CH = 0.01 M. We get have already treated: we neglegt the weak
x = 10−4.75 × 0.1/0.01 = 1.8 10−4  CH and base and calculate pOH for the OH− excess.
thus The case with a weak base, say acetate ion,
plus a strong acid, say HCl, is treated anal-
ogously. If the strong acid is depleted, a
pH = − log(CH + x) ' −logCH (25) buffer results. If the weak base is depleted,

which evaluates to 2.00. Thus when a strong we calculate pH from the excess HCl.
acid is present together with a weak acid, we pH in polyprotes
may neglect the contribution from the weak An acid like H CO is a weak acid with re-
2 3
acid. spect to donoring a proton to water. The re-
By the same reasoning, we may neglect the sult is the corresponding base, HCO3 , which
−

contribution from a weak base in the pres- in turn, however, may also donate a proton
ence of a strong base, like OH− . to water, and thus react as an acid as well.
The two corresponding ionization constants
pH in weak acid plus strong base
are known as Ka1 and Ka2 respectively. In
Consider a mixture of 8.0 mL 0.200 M am- general, for a diprote acid H2 A we have
moniumchloride NH+ 4 , Cl
−
and 2.00 mL of
0.100 M NaOH. We have
[H3 O+ ][HA− ]
C(NH+ 4 ) = 1.60/10.0 = 0.16 M and K a1 = (27)
C(OH ) = 0.2/10.0 = 0.020 M.
− [H 2 A]

NH+ + [H3 O+ ][A2− ]

4 is a weak acid (HA ) with pKa = 9.25. Ka2 = (28)
Its corresponding base is ammonia NH3 . We [HA− ]
thus get For a solution of H A with nominal con-
2
HA+ + OH−
A centration Ca it is usually a sufficiently good
(I) 0.16 0.02 - approximation to treat the acid, as if only
(II) 0.16 - 0.02 0 0.02 the first dissociation takes place, and thus
The result is thus a solution, which main- ignore the second. For H2 CO3 pK1 = 6.37
ly consists of a weak acid and its correspond- and pK2 = 10.70. For Ca = 0.100M we get
ing weak base, that is, a buffer. We thus get
pKa1 + pC 6.37 + 1.00
nOH− pH = = = 3.69
pH = pKa + log 2 2
nHA+ − nOH− (29)
To see that this is close to the required re-
= 9.25 + log(2/14) = 8.40 (26) sult, we may estimate, how much the second

3
dissociation contributes. Let x = 10−3.69 . The two pK values, which appear in this
For the second step we have formula are the pK , in which the ampholyte
HA− + H2 O
A2− + H3 O+ is the corresponding base (pKa1 here) and
x x the ampholytes own acid ionization constant.
x−y y x+y H3 PO4 is a triprote, and the species H2 PO−
4
Our assumption is that y  x. From and HPO2− 4 are both ampholytes. For a so-
Ka2 we obtain lution of Na2 HPO4 we thus get
pH = (pKa2 + pKa3 )/2.
y(x + y)
Ka2 ' (30) pH in weak polyprotes plus strong acid
x−y
A mixture of 50.0 mL 0.200 M Na2 HPO4
or y = Ka2 = 10−10.7 which is indeed much
and 30.0 mL 0.100 M HCl contains 10 mmol
less than x.
Na2 HPO4 and 3 mmol HCl. We let the
Analogously, a weak diprote base (like A2− strongest acid react with the strongest base,
above) may also be treated as a monoprot and thus H+ reacts with HPO2− 4 . The am-
for the estimation of pOH. Thus for a 0.100 pholyte is in excess, and we end up with
M solution of sodium carbonate, Na2 CO3 , a solution containing 3.0 mmol H2 PO− 4 and
the ion CO2−3 is a weak base with 2−
7.0 mmol HPO4 . This is a buffer, for which
pKb = 14.0 − pKa2 = 14.0 − 10.7 = 3.3. we compute pH = pKa2 + log(7.0/3.0).
pH in ampholytes Had we used equimolar amounts, say
Whereas H2 CO3 may be treated as a mono- 10 mmol of each, HPO2− 4 had been con-
prote acid, and Na2 CO3 as a monoprote base, verted to 10.0 mmol of H2 PO− 4 . The result

the hydrogencarbonate ion HCO− is a solution of an ampholyte, with

3 is both
2−
an acid (forming CO3 ) and the correspond- pH = (pKa1 + pKa2 )/2.
ing base (to H2 CO3 ). Such species are known If we had used 60.0 mL 0.200 M HCl in-
as amphiprotes or ampholytes. stead, we now start with 12.0 mmol HCl.
10 of these are used to convert HPO2− 4 to
Consider a solution of NaHCO3 in water.
10.0 mmol H2 PO− 4 . The 2.0 mmol HCl ex-
If we use the principle above and let the
cess then reacts further with the strongest
strongest acid react with the strongest base,
base present, which is now H2 PO−4 and the
we have: HCO− 3 is the strongest acid present,
end result is 8 mmol H2 PO4 and 2.0 mmol
−
and HCO− 3 is the strongest base as well. We
H3 PO4 , which is again a buffer, this time
thus get
with pH = pKa1 + log(8.0/2.0).
The reaction of weak polyprotes with strong
2 HCO−
3
CO2−
3 + H2 CO3 (31) base like NaOH is treated analogously.

From this it is seen that [CO2− 3 ] ' [H2 CO3 ]

Titration curves
in the solution. Now consider the product If we have a solution of a weak acid, and
slowly add a strong base like NaOH, we shall
2− see that pH increases rapidly, when equimo-
[H3 O+ ][HCO− +
3 ] [H3 O ][CO3 ]
Ka1 Ka2 = lar amounts of the weak acid and strong
[H2 CO−3] [HCO−3] base are approached. This may be used
' [H3 O+ ]2 (32) for volumetric analysis. If the concentration
of the weak acid is initially unknown, the
and thus we have the approximation amount of NaOH may be recorded, where
this pH shift occurs. The original acid con-
tent is then equal to the added base content
pKa1 + pKa2 at the equivalence point.
pH = (33)
2 To construct typical titration curves, we
may start with a weak acid like HAc with

4
 pH
pKa = 4.75 and known concentration 14

C = 0.0100 M, say. A 20.00 mL solution 12

thus contains 0.200 mmol HAc initially. The

NaOH solution with accurate concentration 10

0.1000 M is contained in a burette, a long 8

pKa
narrow cylinder flask graduated to display 6 pOH = pKb +pC
2

the volume used. We will construct the curve 4

displaying pH as a function of mL base added,

see Fig.(1).
2

Initial point. 0 mL base added. 0.0

0 0.2
1.0
0.4
2.0
0.6
3.0
α
mL
0.8 1 1.2 1.4 1.6

As HAc is a weak acid, pH in the initial so-

lution may be estimated using the standard
Figure 1: Titration curve for monoprote
formula Eq.(14).
weak acid
Points before the equivalence point.
To reach the equivalence point, we need
0.200 mmol base, that is 2.000 mL. We will Titration curves for polyprotes.
call this no mL. If we add a fraction α of this
This may be illustrated with the titration of
amount, we end up with a buffer. The ratio
a weak diprote acid H2 A. The calculations
Cb /Ca = (αno /V)/((no − αno )/V) and thus
follow the scheme for a monoprote acid ini-
α tially, notably at α = 0.5 we get pH = pKa1 .
pH = pKa + log (34)
1.0 − α But at the 1. equivalence point, the cor-
independent of the volume in the titration responding base is now the species HA− ,
flask. Note especially that for α = 0.5 we which is an ampholyte, and Eq.(17) is thus
get pH = pKa . At this point the change in replaced by Eq.(33).
pH per mL base is the smallest, and the If we add more NaOH, the first no mmol,
titration curve thus is close to horizontal. corresponding to α = 1.0, are now used
to convert H2 A to HA− , but a new buffer
Equivalence point.
arises for 1.0 < α < 2.0 based on pKa2 . No-
For α = 1.0 all the HAc is converted to
tably, for α = 1.5 we get pH = pKa2 . At
the corresponding base Ac− , and the pH
the second equivalence point, α = 2.0, we
in the solution may thus be estimated from
have a solution of the weak base A2− with
Eq.(17). We now have
pKb = 14.0 − pKa2 . For α > 2.0 we are left
Cb = no /V ' no /(Va + VNaOH ). Note that
with an excess of the strong base, as before.
pH generally is not equal to 7.0 at the equiv-
pH
alence point. From the displayed curve, we
14

see that the buffering capability of the solu-

tion is gone now, and pH increases substan- 12

pKa2
tially at the equivalence point. Thus the 10

curve is near-vertical here. 8

pKa1
Points past the equivalence point. 6 pOH = pK 2+pC b

For α > 1.0, we have used no mmol to con- 4

vert HAc to Ac− , and the excess of strong pK +pK a1 a2

2 2
base is then (α − 1)no mmol. F. ex. if we
add 2.500 mL NaOH, the excess is 0
0 0.5 α 1 1.5 2 2.5

0.500 × 0.1000 = 0.0500mmol and the vol-

ume is 22.5 mL. Thus [OH− ] = 0.0500/22.5
from which pOH is calculated. Asymptoti- Figure 2: Titration curve for diprote weak
cally, pH approaches the pH of NaOH in the acid with pKa1 = 4.0 and pKa2 = 8.0.
burette, which is 14.0 -1.0 = 13.0 here.

5
The curve is thus approximately flat around
α = 0.5 and α = 1.5, but rises sharply at the 1

two equivalence points, with α = 1.0 and α = [s]/C 1 − α = [b]/C

0.8
α = 2.0, see Fig.(2). However, if some of
the pK’s are close together, there is too little 0.6

space to manifest the vertical character at pKI

the equivalence point in between. The curve 0.4

thus appears to go from one near-horizontal 0.2

buffer zone into another such flat zone, with-

out a pronounced vertical part. The same 0
0 2 4 6 8 10 12 14 pH
may occur, if some of the pK’s are close to
either 0 or 14.
Figure 3: Bjerrum diagram for a weak
Indicators monoprote acid. The fraction of acid
pH may be measured in an electrochemical α = [s]/C as a function of pH is shown. The
cell, and this will be discussed in the text corresponding base fraction is 1 − α. At
on electrochemistry. It is thus possible to pH = pKa both fractions are equal to 1/2.
follow the pH change and record the fast An indicator I may shift color, when pH
pH changes automatically. changes past pKI ≡ pKa .
It is possible also to determine the pH chan-
ge visually. Some weak acids, and/or their
bases, are very strongly colored. A small the system appears green. However, if a
insignificant amount of such a substance to drop of this indicator system is added to
the solution under investigation will not chan- a system under titration, initially the solu-
ge pH appreciably. If the small total con- tion may be on the acidic side of pKI and
centration present is C = [s] + [b], we may thus blue. When pH changes past pKI , the
rewrite the expression for the indicators ion- color changes to yellow. If an indicator has
ization constant in terms of the fraction been chosen with pKI close to the pH of the
α = [s]/C. equivalence point, and pH changes rapidly
here, one drop of NaOH may be sufficient for
the indicator to switch color substantially.
[H3 O+ ][b] [H3 O+ ](1 − α)
KI = = (35) This then reveals that the equivalence point
[s] α
was passed, and the burette reading may be
and thus recorded.
(1 − α) PC programs
pH = pKI + log (36)
α
The approximation formulas above are not
This is superficially like the buffer equation,
always satisfactory. For accurate work, it
but the latter only holds for pH near pKa of
is possible to write up a balance equation,
the buffer system, whereas Eq.(36) is valid
which involves all species of relevance to the
for all pH, since it is simply a logarithmic
problem. Usually this results in a polyno-
version of the expression for the ionization
mial equation of quite high order (a fifth or-
constant, in terms of the actual fractions of
der polynomial, say). It is, however, an easy
the acid or base. Here, one of these fractions
task to let the computer search iteratively
may be very small.
for pH values, which satisfy this equation.
If α is displayed from Eq.(36) as a function
While such a procedure may yield val-
of pH, α is close to one on the acidic side
ues in better agreement with experimentally
of pKI , whereas α drops to near zero on the
recorded pH values, qualitative features may
basic side of pKI . See Fig.(3).
be studied on the basis of the simplified for-
Suppose now that s is deep blue, whereas mulas discussed above.
b is deep yellow. If pH is close to pKI ,