ECOLE NATIONALE POLYTECHNIQUE

Département des Classes Préparatoires

Année universitaire 2020/2021

Chapter II _ACID-BASIC EQUILIBRIA (Part 2)

5) Case of ampholytes

An ampholyte is a chemical species that can behave as both an acid and a base
in aqueous solution.
Consider a solution of an HA- ampholyte of concentration c. HA- is the base of
the H2A/HA- couple (pKa1) and the acid of the HA-/A2- couple (pKa2)

Three reactions involving HA– occur; let K1, K2 and K3 be their constants:
(1) 2 HA– = H2A + A2– K 1 = Ka2 /Ka1
(2) HA– + H2O = A2– + H3O+ K2= Ka2
(3) HA– + H2O = H2A + HO– K3 = Kb1 = Ke /Ka1
(*)Note: Ampholyte HA– can participate in three reactions:
(1) HA– dismutates;
(2) HA– is an acid;
(3) HA– is a base.
When, the constant K1 is significantly greater than K2 and K3 (K1 > 100. K2
and K 1 > 100. K3); reaction (1) is the predominant reaction: it imposes the pH
of the solution.

Its equilibrium constant is: K1 = [H2A][A2-]/ [HA-]2 = Ka2/Ka1

(1) being the predominant reaction, its gives [H2A] = [A2–].

The Ka2. Ka1 product which is written : Ka2.Ka1= ([H3O+][ A2-]/[HA-

])([H3O+][HA-]/[ H2A])= [H3O+]2[ A2-]/[ H2A]= [H3O+]2

pH = 1/2 (pKa1 + pKa2)

Note: For an Ampholyte, the pH is independent of the initial concentration.

6) Case of polyacids (polybases):

A polyacid (diacid, triacid, etc.) successively participates in several acid-base
pairs of different pK, by releasing its protons. It thus behaves like a mixture of

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acids, for which the strongest acid imposes the hydronium ion concentration.
and therefore the pH of the environment.
Common polyacids are weak. In addition, we generally observe that:

Ka1> Ka2 >Ka3  pKa1 <pKa2 <pKa3

When the first two pKa are at least two units apart: only the first acidity (lowest
pKa) is to be taken into consideration, and the calculation is carried out as for a
monoacid. Otherwise, the analysis leads to a complex equation. Likewise for
polybases, analytical resolution is only possible if the strongest basicity (highest
pKa) can be taken into account alone, the calculation will then be carried out as
for a monobase.
∆ pKa = ǀ pKa2 – pKa1ǀ ≥ 2
We consider the 1st acidity for a polyacid (smallest pKa)
We consider the 1st basicity for a polybase (highest pKa)

Example : Calculate the pH of a 10-2 M solution of phosphoric acid H3PO4.

We have the following equilibria in aqueous solution:
1) H3PO4 (aq) + H2O ⇌ H2PO4-(aq) + H3O+ (aq) ; Ka1 = 7.59·10-3 ; pKa1 = 2.12
2) H2PO4-(aq) + H2O ⇌ HPO42-(aq) + H3O+ (aq) ; Ka2 = 6,17·10-8 ; pKa2 = 7,21
3) HPO42-(aq) + H2O ⇌PO43- (aq) + H3O+ (aq) ; Ka3 = 4.27·10-13 ; pKa3 =12.37
Solution :
Method 1 : ∆ pKa = ǀ pKa2 – pKa1ǀ ≥ 2  We only consider the first acidity of
H3PO4 (Case of a weak acid).
Method 2 :
 We neglect the 2nd acidity (H2PO4- weakly dissociated) if
pH ≤ pKa2 – 1
 We neglect the 3rd acidity (HPO42- weakly dissociated) if
pH ≤ pKa3 – 1
 We only consider the 1st acidity:
x (x+ξ)
H3PO4 (aq) + H2O ⇌ H2PO4-(aq) + H3O+ (aq) ; Ka1 =
Ca−x)

à t=0 Ca 0 ξ

à teq Ca - x x x+ ξ
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H3PO4 is treated as the case of a weak acid :

 We neglect the water’s autoprotolysis if pH ≤ 6,5, ξ = 0.

 H3PO4 is weakly dissociated if pH ≤ pKa - 1 , x<<< Ca

Note 1 : The approximations must be checked at the end of the calculation. The
pH must meet the conditions:

 pH ≤ 6,5
 pH ≤ pKa1 – 1
 pH ≤ pKa2 – 1
 pH ≤ pKa3 – 1
Note 2 : If HnA is considered a strong polyacid, it comes:
pH = - log nCa

Likewise for a strong polybase:

pH= 14+ log nCb

7) Calculation of pH of mixtures
a) Mixture of two strong acids
HA1 is a strong acid of concentration C1
HA2 is a strong acid of concentration C2
HA1 + H2O → A1- + H3O+
HA2 + H2O → A2- + H3O+
H3O+ + OH - ⇄ 2H2O

[H3O+]T = C1+ C2

pH = - log (C1’+C2’)

b) Case of a mixture of two strong bases

B1 + H2O → B1H+ + OH-
B2 + H2O → B2H+ + OH-
pH = pKe + log(C1’+C2’)

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c) Case of a mixture of a strong acid and a weak acid.

Let the two acids
HA1a strong acid HA2 a weak acid
Concentration C1 Concentration C2,
Volume V1 Volume V2, Acidity constant
Ka

After mixing the two acids, the dilutions must be taken into account:

𝐶1′=𝐶1×𝑉1/𝑉1+𝑉2 et 𝐶2′=𝐶2×𝑉2/𝑉1+𝑉2

1. If C’1 and C’2 are close: it is the strong acid HA1 which is
predominant

HA1 + H2O → A- + H3O+ pH = - log C’1

2. If C’1<< C’2: the weak acid HA2 must also be taken into account:

HA1 + H2O → A1- + H3O+

HA2 + H2O ⇄ A2- + H3O+ ; 𝐾𝑎 = [H3O+][𝐴2−]/[𝐻𝐴2]

à t=0 C’2 0 C’1 + ξ

à teq C’2 - x x C’1 + x + ξ

𝐾𝑎= (C’1 + x + ξ) x
d) Case of a mixture of two weak acids

Let the following two weak

acids be
HA1 a weak acid HA2 a weak acide faible
Concentration C1 Concentration C2,
Volume V1 Volume V2,
Acidity constant Ka1 Acidity constant Ka2

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1. If pKa2 – pka1 ≥ 4 HA1 is stronger than HA2, then HA1 is the

predominant:
HA1 + H2O A-1 + H3O+ , With [HA1]o = C1
After mixing the two acids, the dilutions must be taken into account:
𝐶1′=𝐶1×𝑉1/𝑉1+𝑉2

Likewise the pH will be that of a weak acid

2. If pKa2 – pKa1< 4 : we must take into account the 2 acids:

HA1 + H2O A-1 + H3O+ [HA1]0 = C1

HA2 + H2O A-2 + H3O+ [HA2]0 = C2

After mixing, the concentrations become

:
𝐶1′=𝐶1×𝑉1/𝑉1+𝑉2 et 𝐶2′=𝐶2×𝑉2/𝑉1+𝑉2

𝐾𝑎1=[H3O+][𝐴1−]/[𝐻𝐴1] et 𝐾𝑎2=[H3O+][𝐴2−]/[𝐻𝐴2]
[H3O+]T = [A-1] + [A-2]
C.M. If HA1 and HA2 are very little dissociated. [HA1] ≈ C’1 et [HA2] ≈ C’2

𝐾𝑎1=[H3O+][𝐴1−]/𝐶′1 𝐾𝑎2=[H3O+][𝐴2−]/𝐶′2
[𝐴1−]=𝐾𝑎1𝐶′1/[H3O+] [𝐴2−]=𝐾𝑎2𝐶′2/[H3O+]
[H3O+]=𝐾𝑎1𝐶′1/[H3O+]+𝐾𝑎2𝐶′2/[H3O+]
[H3O+]2=𝐾𝑎1𝐶′1+𝐾𝑎2𝐶′2

𝐩𝐇=−𝟏/𝟐log ((𝐊𝐚𝟏𝐂′𝟏+𝐊𝐚𝟐𝐂′𝟐)

e) Case of an acid-base mixture:

See acid-base titrations.

Buffer solutions

3.1. Definition of a buffer solution

A buffer solution is a solution that consists of an “equimolecular” mixture of a
weak acid HA and its conjugate base A-.
3.2. Property of the buffer solution
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A buffer solution is characterized by a constant pH. It makes it possible to fix the

pH of a reaction medium.

A solution has a buffer effect if its pH varies very little:

– by adding small quantities of hydronium ions or hydroxide ions provided by

acids or bases which may be strong;

– by moderate dilution.

The buffering power of a solution is reflected by its capacity to “buffer”, that is

to say its ability to oppose variations in pH upon the addition of H3O+ or OH-
ions. This capacity is defined as the quantity Q of H3O+ protons or OH- ions
which, added to 1 liter of the solution, causes a pH variation of 1 unit around
the pKa.

𝑑𝐶𝑂𝐻 𝑑𝐶𝐻3 𝑂+
𝛽=| |=| |
𝑑𝑝𝐻 𝑑𝑝𝐻

Practically, the buffer mixture retains its properties as long as :

[𝐴− ]
0,1 ≤ [𝐻𝐴] ≤ 10 and therefore pH between : 𝑝𝐾𝑎 − 1 < 𝑝𝐻 < 𝑝𝐾𝑎 + 1

La The concept of buffer power was introduced by Van Slyke in 1922.

The buffering power β is expressed as mol. L–1.

Note :
The larger β is, the more effective the buffer is; β depends on the acidic and
basic species considered and their concentrations.
Preparation of the buffer solution
Three methods:
1. we mix a solution S1 of the weak acid AH and a solution S2 of the weak base
A-.
2. we mix a solution S1 of the weak acid AH and a solution S2 of strong base:
we partially neutralize the solution of the weak acid.
3. we mix a solution S1 of the weak base A- and a solution S2 of strong acid: we
partially neutralize the solution of the weak base
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In all cases, the concentration [AH] of the weak acid and the concentration [A-]
of the weak base must be close: [AH] ≈ [A-]
Example :

• by mixing close concentrations of a weak acid (CH3COOH) and a salt of

its conjugate base (CH3COONa).

• by a mixture of concentrations close to a weak base (NH3) and a salt of

its conjugated acid (NH4Cl).

Calculation of pH of buffer solution

HA and A-species are in equilibrium: HA + H2O H3O+ + A-

𝐾𝑎=[H3O+][𝐴−]/[𝐻𝐴]

[H3O+]=𝐾𝑎[𝐻𝐴/][𝐴−]

Equation of Henderson- Hasselbalch : =𝑝𝐾𝑎+log ([𝐴−]/[𝐻𝐴])

𝑝𝐻=𝑝𝐾𝑎+log ([𝐵𝑎𝑠𝑒]/[𝐴𝑐𝑖𝑑𝑒])

Si [𝐻𝐴]=[𝐴−] alors 𝒑𝑯=𝒑𝑲𝒂.

Note:
(*) A solution of strong acid or strong base at a pH not very sensitive to addition

moderate amount of hydronium ions or hydroxide ions. On the other hand, its
pH clearly depends on the dilution. A solution of strong acid or strong base,
which therefore only meets one of the two conditions for defining a buffer
solution, is a pseudo-buffer.

(**) Many biological media are buffered. So the blood is

buffered at pH = 7.4 at 37 °C by the couples: H2PO4– / HPO4 2– and CO2 /

HCO3–.

(***) Practically, the buffer mixture retains its properties as long as:

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[𝐴− ]
0,1 ≤ [𝐻𝐴] ≤ 10aand therefore its serum pH includes between:

𝑝𝐾𝑎 − 1 < 𝑝𝐻 < 𝑝𝐾𝑎 + 1

Example 1 :

Either the monosodium phosphate - disodium phosphate buffer mixture:

H2PO4- + H2O ⇄ HPO42- + H3O+ (pKa = 7,2)

If to such an equimolar mixture of pH=7.2, hydrochloric acid is added to a

concentration of 0.1M, the pH becomes:
pH = 7,2 + log [HPO42-] / [H2PO4-]= 7,2 + log (1-0,1) / (1+0,1) = 7,1
If we dissolve 0.1 mole of strong acid (HCl acid) in a liter of pure water, then
the pH goes from 7 to 1. By carrying out the same operation no longer in a liter
of water, but in a liter of aqueous solution of monosodium phosphate at
1mole.L-1 and disodium phosphate at 1mole.L-1, the pH goes from 7.2 to 7.1.
This limitation of pH variations is called the “buffer effect”.
Le Châtelier's principle explains such a phenomenon:
The addition of a strong acid disrupts the acid-base balance of the weak acid and
its conjugate base. There is therefore an evolution of the system towards a new
state of equilibrium, opposing the disturbance. In this case, the conjugate base of
the weak acid will consume the hydronium ions H3O+, which have been added.
Note:

To create a buffer solution of a given pH, it is recommended to choose an

acid-base pair with a pKa close to the desired pH.
Buffer solutions are very important for living species. They help them to
resist sudden variations in the environment. An example of a buffer solution

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is the stomach. No matter what we eat or drink, its pH is almost not affected.
In our body enzymes are effective in a given pH region.

Also, to keep them effective, the pH must be kept constant in these areas by
buffer solutions.

Example 2 :

1) Let us calculate the pH of a solution containing 0.4 M of formic acid HCO2H

and 0.1 M of its conjugate base HCO2Na with pKa = 3.75. Conclude.
Solution :
pH = pKa + log [B] / [A] = 3,75 + log (0,1 / 0,4) = 3,14

Example 3 :

2) Let's determine the pH:

a) a 0.01 M HCl hydrochloric acid solution
b) a mixture of a solution of hydrochloric acid HCl at 0.01 M with a solution of
acetic acid and sodium acetate [CH3CO2H] = [CH3CO2Na] = 0.1 M. (pKa = 4
,8). Conclude.
Solution :
a) [H3O+] = 0,01 M Then pH =- log [H3O+] = 2
b) Tampon CH3CO2H/ CH3CO2Na :
pH = 4,8 + log [(0,1 – 0,01) / (0,1 + 0,01)] = 4,71.

IV. Acid-base titrations

 Objective :

The objective of such a titration is to find the concentration of an acidic or basic

solution. To do this, we will exploit the pH variations associated with acid-base
transformations.

Experimental device for pH-metric monitoring of the titration of an acid:

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 Determination of the coordinates of the equivalence point:

• The pH evolution curve during the titration of an acid with a base is an increasing
curve presenting a particular zone, called "pH jump", for which the pH rises
suddenly..

• The method for determining the coordinates of the equivalence point from the
pH = f (Vb) curve, called the “parallel tangent method”, consists of drawing two
parallel tangents on either side of the pH jump, then draw a third line equidistant
and parallel to the first two :

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 Summary:
The expressions for pH as a function of the chemical species are given as
follows, taking into consideration the two approximations seen above:
 Strong acid : pH = - log Ca
 Weak acid : pH = ½ pKa – ½ log Ca
 Strong base : pH = 14 + log Cb
 Weak base : pH = ½ (14 + pKa + log Cb)

1) Titration of a strong acid with a strong base

A volume VA, measured with a pipette, of hydrochloric acid solution of

unknown concentration CA is introduced into a beaker.

Known volumes VB of sodium hydroxide solution of concentration CB

are introduced using a burette.

The pH of the mixture is measured by a pH meter.

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Note
• we observe that around the equivalence the pH varies suddenly: we
speak of a pH jump.
• at equivalence the concavity of the curve changes and the curve is
practically symmetrical around E (point of inflection).
Exploitation of experimental results:
1. Before adding the base:
The pH of the solution is that of a strong acid: pH = -log C1

2. If n(H3O+) > n(OH-) (before the equivalent point (E.P)

A part of the H3O+ ions is neutralized by the OH- ions, the remaining number
of H3O+ moles is:
n(H3O+)= C1V1 - C2V2 =(n(H3O+)i - (nOH-)
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[𝐻3𝑂+]=𝐶1𝑉1−𝐶2𝑉2/𝑉1+𝑉2
Then 𝒑𝑯= −𝐥𝐨𝐠 (𝑪𝟏𝑽𝟏−𝑪𝟐𝑽𝟐/𝑽𝟏+𝑽𝟐)

3. At the equivalence: Na Va = Nb Vb
n(H3O+) = n(OH-)
The neutralization is total, the pH of a neutral salt.
[H3O+] = [OH-] = 10-7 mole.l-1 PH = 7.
When titrating a strong acid with a strong base, the pH at the
equivalent point is neutral.

4. If n(OH-) >n(H3O+) (after the E.P)

All H3O+ ions are neutralized and excess OH- ions remain:
n(OH-)remaining = (nOH-)poured - (n(H3O+)i = C2V2 – C1V1

[𝑂𝐻−]=𝐶2𝑉2−𝐶1𝑉1/ 𝑉1+𝑉2

𝑝𝑂𝐻=−log (𝐶2𝑉2−𝐶1𝑉1/𝑉1+𝑉2)

𝒑𝑯=𝟏𝟒+𝐥𝐨𝐠 (𝑪𝟐𝑽𝟐−𝑪𝟏𝑽𝟏/𝑽𝟏+𝑽𝟐)

2) Titration of a weak acid with a strong base

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Note
• the curve pH = f(Vb added) admits two points of inflection, of the same
pHE > 7 where the acid dosed is weak
• We observe a jump in pH at equivalence but it is less significant than when
dosing a strong acid.
• The pH at equivalence is basic (8.6 for CA = CB = 1.0.10-2 mol.L-1)
• The volume VB = 10 mL corresponds to the half-equivalence: the pH is
equal to the pKA of acetic acid: 4.8
• The curve is curved for weak VB, unlike what happens with a strong acid
. Exploitation of experimental results:
The titration of a weak acid is carried out using a strong base and follows the same
principle as above.

Example : Titration of acetic acid with sodium hydroxide.

The reaction is:

his reaction is total.

i. Before the titration the pH of the acetic acid solution is given by the relation
of a weak acid:

However, the pH at equivalence is not neutral but basic. All the acetic acid and
NaOH are consumed but the acetate has been produced and it is a weak base.

ii. Before equivalence, the pH depends on the quantity of weak acid and its
conjugate base:

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This mixture between a weak acid and its conjugate base is called a buffer
solution because the addition of a strong base or acid does not significantly
change the pH of the solution.La demi-équivalence est le moment où il y a
autant de CH3COOH que CH3COO–. À ce stade pH = pKa.

Note : To reach the half-equivalent point, the added volume of the base is
half the volume to obtain the equivalence.

iii. At equivalence the pH is given by the quantity of acetate in the solution

(weak basic salt: formula for a weak base. This quantity is equal to that of
NaOH added to the solution.

iv. After the equivalence point the pH is given by the excess amount of NaOH
in the solution.

Note :
The concentrations must be recalculated in the mixture.

3) Influence of acid strength

Let's compare two weak acids of the same concentration but different
pKA (as well as a strong acid to complete the comparison):
We observe that the jump in pH is more marked as the acid is stronger.
This pH jump becomes difficult to detect for a very weak acid (pKA > 9)

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4) Influence of the concentration on the shape of the dosage curve

Let us superimpose the dosage curves obtained for concentrations of acetic acid
CA1 = 1.00.10-1 mol/L; CA2 = 1.00.10-2 mol/L; CA3 = 1.00.10-3 mol/L

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We notice that the jump in pH is all the more marked as the concentration is
greater.

5) Acid-base colored indicators

These are pairs (weak acid/weak base) whose conjugated species have
different colors.

If we note (HIn / In-) and Ki the acidity constant of this couple, we admit that
the color of the solution is that of the acid form HIn if the concentration of
acid form HIn is at least 10 times greater than that of the basic form In-.

 Turning area
Between pKi -1 and pKi +1, that is to say over two pH units, the color is a
mixture of the acidic color and the basic color: this is the turning zone.
 Predominance diagram

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ANNEX
The titration of a polyacid:
Consider a polyacid HnA (a concrete example will be given later), the
neutralizations of the different forms of the acid are successive: the base OH–
will first neutralize the protons released by HnA then the protons released by
Hn-1A– etc. …..

The initial pH of the solution is the pH of HnA. Concentrations of the

followingacids are negligible. HnA can be a strong acid or a weak acid.

At the first equivalence point Hn-1A– is the main species in solution. It is an

amphoteric species, meaning it can accept or donate protons. The pH is as
follows:

At the next half-equivalence point, [Hn-1A–]=[Hn-2A2-] and we are in a buffer

solution. Remember that the pH in buffer solutions is

The pH is therefore pH =pKa2. Note that if the initial acid is a weak acid the
same is true for the first half-equivalence point, namely pH =pKa1. It is
interesting to note that, for these particular values, pH does not depend on
concentration.

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Let’s take the case of H3PO4 as an example:

The neutralizations are successive and we can thus find the specific points (half-
equivalences and equivalences) determined above

i. H3PO4 is a weak acid. The initial pH of the solution is therefore:

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Before the equivalence, H3PO4 and H2PO4– are in solution. This buffer
solution has a pH of

With pH = pKa1, when [H3PO4] = [H2PO4–], at half-equivalence.

ii. At the first equivalence, H2PO4– is the main species in solution. It is

an amphoteric species and the pH will therefore be:

iii. After the first equivalence, H2PO4– and HPO42– are in solution. This is
still a buffer solution.

Avec pH = pKa2 lorsque [H2PO4–] = [ HPO42-], soit à la deuxième demi-

équivalence.

iv. At the second equivalence point HPO42- is the main species in solution
and is amphoteric.

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v. After this equivalence, the solution is again a buffer solution.

With pH = pKa3 when [HPO42-] = [PO43-], this is the third half-equivalence.

vi. At the third equivalence PO43- is the main species in solution. It is not an
amphoteric species but a weak base. The pH is written::

However, Ka3 is very close to Ke. Consequently, the neutralization of the third
acidity will not appear on the curve.

Note :
The concentrations must be recalculated in the mixture.

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