Calculating the Concentration of H3O+ (pH)

in Aqueous Solutions of Salts

Problem 1:
Calculate the pH of 0.20 M NaNO2 (Ka for HNO2 is 4.6×10–4).
Solution:
NaNO2 is a salt of a strong base NaOH and weak acid HNO2 .
In an aq. solution, it is completely dissociated into Na+ and NO2- ions.
The principal equation for NaNO2 interaction with water:
NO2– + H2O(l) HNO2 + OH– base dissociation rxn; Kb
Note: Na+ as a strong base cation does not react with water.
Note: This
Kb (for NO2 = [HNO2][OH–]/[NO2–]
–) = Kw/Ka(for HNO2) = problem is about
= (1.0×10–14)/(4.6×10–4) = 2.2×10–11 finding the pH of
a weak base.
The initial concentration of NO2–, CNO2- = 0.20 M.
Define X the concentration of NO2– that undergoes hydrolysis.
Then, the equilibrium concentrations are: [HNO2] = [OH–] = X;
[NO2–] = CNO2- – X  CNO2- = 0.20 M
Kb = X2/ 0.20 = 2.2×10–11; X =  (2.2×10–11)× 0.20 = 2.1×10–6
Hence, [OH–] = 2.1×10–6 M;
[H3O+] = Kw/[OH–] = 1.0×10–14/2.1×10–6 = 4.8×10–9 M;
pH = – log[H3O+] = – log (4.8×10–9) = 8.32.
Problem 2:
Calculate the pH of 0.20 M NH4NO3 (Kb for NH3 is 1.8×10–5).
Solution:
NH4NO3 is a salt of a weak base NH3 and strong acid HNO3 .
In aq. solution, it is completely dissociated into NH4+ and NO3- ions.
NO3- as the anion of the strong acid does not react with water.
The principal equation for NH4NO3 interaction with water:
NH4+ + H2O(l) H3O+ + NH3 acid dissociation rxn; Ka

Ka (for NH4+) = [H3O+][NH3]/[NH4+] = Kw/Kb(for NH3) = Note: This

problem is about
= (1.0×10–14)/(1.8×10–5) = 5.6×10–10
finding the pH of
The initial concentration of NH4+, CNH4+ = 0.20 M. a weak acid.
Define X the concentration of NH4+ that undergoes hydrolysis.
Then, the equilibrium concentrations are: [NH3] = [H3O+] = X;
[NH4+] = CNH4+ – X = 0.20 – X;
since CNH4+>>Ka, X is very small and hence, we may assume that
[NH4+]  CNH4+ = 0.20 M;
Ka = X2/ 0.20 = 5.6×10–10; X =  (5.6×10–10)× 0.20 = 1.06×10–5;
Hence, [H3O+] = 1.06×10–5 M;
pH = – log[H3O+] = – log (1.06×10–5) = 4.97.
 Common Ion Effect on Acid-Base Dissociation:
Mixing a Weak Acid and Its Conjugate Base
A weak acid HA dissociates in aqueous solution:
HA + H2O H3O+ + A–.
If some amount of a soluble salt of this acid, MA, is added to the
solution, the concentration of A– ions in this solution increases.
A– is called the common ion, since it is “common” for both
the acid and the salt. At the same time, A- is the conjugate base to HA.
Just a tip: To predict the effect of common ion on equilibrium,
recall Le Châtelier’s principle.
In accordance with Le Châtelier’s principle, the equilibrium shifts to the
left:
HA + H2O H3O+ + A–.
Therefore,
the presence of common ion suppresses dissociation of a weak acid,
which decreases the concentration of H3O+ ions (pH becomes higher).
 Acid-Base Buffer Solutions

An acid-base buffer is a solution that diminishes changes in pH from addition

of acid or base.
When a relatively small amount of H3O+ (acid) or OH– ions (base) is added to a
buffered solution, the change in pH is much smaller than the change that
results from the same addition to an unbuffered solution.

Most commonly, the components of a buffer are the conjugate acid-base pair
of a weak acid or weak base.
Examples:
CH3COOH and CH3COO–
acid base
– 2–
H2PO4 and HPO4
acid base
HF and F–
acid base
NH4+ and NH3
acid base
 How Does a Buffer Work?
A buffer consists of high concentrations of a conjugate acid-base pair,
HA and A–, in aqueous solution:
Ka [H3O+][A-]
HA + H2O H3O+ + A- Ka =
[HA]
Kb [HA][OH-] Kw
-
A + H2O HA + OH- Kb = =
[A-] Ka

A buffer works via the common-ion effect:

○ When a small amount of H3O+ or OH– is added, a small amount of
one buffer component converts into the other:
 the A– consumes added H3O+ and converts into HA;
 the HA consumes added OH– and converts into A–.

○ This changes relative concentrations of the buffer components,

HA and A–. However, the change is very small as far as the amount
of added H3O+ or OH– is much smaller than the initial concentrations
of HA and A– in the buffer.
○ Due to this, the added ions H3O+ or OH– have only little effect on the pH.
In a buffer solution, [H3O+] = Ka ([HA]/[A-]) ≈ Ka (CHA/CMA).
For example, a buffer made with equal, large concentrations of HF and F-:

♦ If a small amount of OH- is ♦ If a small amount of acid is

added, HF reacts with the OH− to added, the F− reacts with it to
make F− and water. form HF and water.

The effect on pH is very small.

 The pH of a Buffer: The Henderson–Hasselbalch Equation
For a weak acid, equation of dissociation in aqueous solution,
HA + H2O(l) H3O+ + A–,
[H3O+] [A–]
is characterized by the equilibrium constant Ka =
[HA]
+
[HA]
After the rearrangement: [H3O ] = Ka x
[A–]

Taking the negative log of both sides of the above formula gives:
–log [H3O+] = – log Ka – log ([HA]/[A–]) = – log Ka + log ([A–]/[HA]).
With –log [H3O+] = pH and –log Ka = pKa, the eqn is modified as:
[A-]
pH = pKa + log
[HA]
or, using the conjugate acid-base terminology,

[base] the Henderson-Hasselbalch

pH = pKa + log
[acid] equation
 [base] the Henderson-Hasselbalch
pH = pKa + log
[acid] equation

Important note: A buffer is a mixture of a weak acid (or weak base)

and its salt (e.g., the conjugate base or acid, respectively), both of which are
present in solution in relatively high concentrations.

Since the initial concentrations of the buffer components usually are much larger
than the numerical value of the Ka (or Kb), we may use an approximation
that in the Henderson-Hasselbalch eqn., [acid]  Cacid and [base]  Cbase.

[base]
pH = pKa + log  pKa + log (Cbase/Cacid)
[acid]
Problem 1:
Calculate the pH of a buffer solution which is 0.25 M in HF
(Ka = 3.5×10–4) and 0.50 M in NaF.
Solution:
Dissociation of HF in water: HF + H2O H3O+ + F-

[base] [F-]
pH of a buffer: pH = pKa + log = pKa + log
[acid] [HF]
[HF] ≈ CHF = 0.25 M;
[F–] ≈ CNaF = 0.50 M.
Substituting into the H.-H. equation:
pH = -log(3.5×10–4) + log(0.50/0.25) = 3.76
Problem 2:
A buffer solution was prepared by dissolving 0.24 moles of NH3 and
0.20 moles of NH4NO3 in 1.00 L of water. Kb(NH3) = 1.8×10-5.
What is the pH of this buffer?
Solution:
NH3 is a weak base which dissociates in water:
NH3 + H2O NH4+ + OH-
The buffer consists of an acid NH4+ and its conjugate base NH3 in
concentrations
CNH4+= 0.20 mol/1.00 L = 0.20 M and CNH3= 0.24 mol/1.00 L = 0.24 M.
[base]
pH = pKa + log = pKa(NH4+) + log(CNH3/CNH4+)
[acid]
Find the pKa for NH4+:
Ka(NH4+) = KW/Kb(NH3) = (1.0×10-14)/(1.8×10-5) = 5.6×10-10;
pKa = -log (5.6×10-10) = 9.26.
Substitute in the H.-H. eqn.:
pH = 9.26 + log(0.24/0.20) = 9.34
 Calculating Changes in the pH of Buffer Solutions Upon Addition of
Strong Acids/Bases

Problem:
Calculate the pH of a buffer solution that is 0.55 M in acetic acid, CH3COOH
(Ka = 1.8×10–5) and 0.35 M in sodium acetate, NaCH3COO.
How will the pH change upon addition to 0.100 L of this buffer solution of
(1) 0.0020 mol of HNO3;
(2) 0.0040 mol of KOH?

Solution:
Dissociation of acetic acid in water:
CH3COOH + H2O(l) CH3COO– + H3O+
Finding pH of the buffer:
pH = pKa(CH3COOH) + log(CCH3COO-/CCH3COOH) =
= -log(1.8×10–5) + log(0.35/0.55) = 4.74 + (-0.20) = 4.54.
pH = 4.54
(a) Upon addition of 0.0020 mol of HNO3 (a strong acid!),
which is equivalent to 0.0020 mol/0.100 L = 0.020 M [H3O+],
the equilibrium in the buffer solution shifts to the left:
CH3COOH + H2O CH3COO– + H3O+(added).
As a result, all added H3O+ (0.020 M) is consumed, at expense of conversion
of the same amount of CH3COO– into CH3COOH.

Therefore, new concentrations are:

[CH3COO–] = 0.35 – 0.020 = 0.33 M and
[CH3COOH] = 0.55 + 0.020 = 0.57 M.

pH = pKa(CH3COOH) + log([CH3COO-]/[CH3COOH] ) =
= -log(1.8×10–5) + log(0.33/0.57) = 4.74 + (-0.24) = 4.50.
pH = 4.50 Compare with
pH = 4.54

Q: For comparison: What would be the pH if same amount of acid

(0.020 M [H3O+]) was added to unbuffered solution?
A: pH = 1.70
(b) Upon addition of 0.0040 mol KOH (a strong base!),
which is equivalent to 0.0040 mol/0.100 L = 0.040 M,
the following reaction takes place:
CH3COOH + OH–(added) CH3COO– + H2O.
As a result, all added OH– is consumed, at expense of conversion of the same
amount of CH3COOH into CH3COO–.

Calculate the new concentrations:

[CH3COO-] = 0.35 + 0.040 = 0.39 M;
[CH3COOH] = 0.55 - 0.040 = 0.51 M.
pH = pKa(CH3COOH) + log([CH3COO-]/[CH3COOH] ) =
= -log(1.8×10–5) + log(0.39/0.51) = 4.74 + (-0.12) = 4.62.
pH = 4.62
Compare with
pH = 4.54

Q: For comparison: What would be the pH if same amount of base

(0.040 M [OH-]) was added to unbuffered solution?
A: pH = 12.60
 The Effect of Dilution on a Buffer pH
Dilution of a buffer has practically no effect on the pH

- until the approximation

Cbuffer components >> Ka
is valid

Initial concentrations of the HA and A- are 1.00 M;

Ka = 1.00×10-4.
 Buffer Capacity

Buffer capacity, b, is defined as the number of moles of a strong

acid (ca) or a strong base (cb) that causes 1.00 L of the buffer solution
to undergo a 1.00-unit change in pH.
d cb d ca
b = =
d pH d pH
Note: Buffer capacity is NOT the same as the buffer pH:
two buffer solutions may have equal pH, but differ in buffer capacity.

• Generally, the higher concentration of the components of a buffer,

the greater the buffer capacity.
• A buffer has the highest capacity when the component
concentrations are equal, which makes [A–]/[HA] = 1:
pH = pKa + log([A–]/[HA]) = pKa + log (1) = pKa.
• Therefore, a buffer which pH is equal to or near the pKa of its
acid component has the greatest buffer capacity.
 Buffer pH Range

• The pH range of a buffer is that range of pH within which the

buffer is efficient.

• A buffer resist changes in pH the most efficiently (has the

largest capacity) when its pH is close to the pKa of the acid
component.

Accordingly,
• The usable pH range for any buffer is within ± 1 pH unit from
it’s acid pKa:
pH = pKa ± 1.
 Preparing a Buffer
Using the Henderson–Hasselbach equation, we may calculate the concentrations
of acid and base required for preparation of a buffer solution with particular pH:

1. Choose the appropriate conjugate acid-base pair.

Recall: A buffer is the most effective when its pH is approx. same as the pKa
of its acid. Therefore, choose a weak acid which pKa is as close as possible
to the desired pH value.
For example:
Assume that you need to prepare a buffer with pH = 3.90.
You are given the following set of week acids to choose from:
-- acetic acid, CH3COOH, Ka = 1.8×10–5 (pKa = 4.74);
-- formic acid, HCOOH, Ka = 1.8×10–4 (pKa = 3.74);
-- hypochlorous acid, HClO, Ka = 3.0×10–8 (pKa = 7.52);
-- chlorous acid, HClO2, Ka = 1.1×10–2 (pKa = 1.96).

For preparation of a buffer solution with pH 3.90, formic acid, HCOOH,

with pKa = 3.74, and its salt, sodium formate (HCOONa) would be the best
choice.
2. Calculate the needed ratio of concentrations for the buffer components.
pH = pKa + log([A–]/[HA]) or
3.90 = 3.74 + log([HCOO–]/[HCOOH]);
Then, log([HCOO–]/[HCOOH]) = 0.16 and
the ratio ([HCOO–]/[HCOOH]) = 1.4.
Therefore, we need 1.4 mol of HCOONa per each 1.0 mol of HCOOH.

3. For a given (desired) volume of the buffer solution, calculate the buffer
concentration in each of the components.
If we need to prepare 1.0 L of the buffer solution, this solution will be
1.4 mol/1.0 L = 1.4 M in HCOONa and
1.0 mol/1.0 L = 1.0 M in HCOOH.
Problem 2: (Preparing a buffer from a weak acid and NaOH)
What volume of 2.00 M NaOH must be added to 300.0 mL of 1.00 M glycolic
acid, HOCH2CO2H, to produce a buffer solution with pH of 4.000?
(Ka = 1.47×10-4).

Solution:
NaOH must be added to glycolic acid to produce the needed amount of sodium
glycolate:
HOCH2CO2H + NaOH → HOCH2CO2Na + H2O
(i) Find the needed mole ratio of salt NaA and acid HA in the buffer:
pH = pKa + log([A–]/[HA])  pKa + log(CA-/CHA);
4.000 = 3.833 + log(CA-/CHA);
log(CA-/CHA) = 0.167; (CA-/CHA) = 1.47;
Hence, (Moles A–)/(Moles HA) = 1.47.
For acid HA in the buffer:
Total (initial) moles of HA = (Moles of A– formed) + (Moles of HA remaining) =
= 300.0 mL/1000 (mL/L) × 1.00 M = 0.300 mol.
(ii) Find the number of moles of NaOH needed:
Note: Number of moles of A– = Number of moles of NaOH
needed for reaction with the acid HA!

(Moles A–) = (Moles NaOH) = X;

(Moles HA remaining) = (Moles HA initial) - (Moles A–) = 0.300 – X;

Substitute in the mole ratio of A– and HA in the buffer:
(Moles A–)/(Moles HA) = X/(0.300 – X) = 1.47;
2.47X = 0.441; and X = 0.179.
Hence, 0.179 mol of NaOH is needed to prepare the buffer.

(iii) Find the volume of 2.00 M NaOH solution needed:

VNaOH = (0.179 mol)/ (2.00 mol/L) = 0.0895 L = 89.5 mL
Summary of general formulas for calculation of [H3O+] with the
approximation of Cinitial >> K:
▪ In a solution of a weak acid HA:
[H3O+] =  Ka CHA

▪ In a solution of a weak base B:

[H3O+] = Kw/ Kb CB

▪ In a solution of a salt (A-) of a weak acid HA:

[H3O+] = Kw/(Kw/Ka) CA-

▪ In a solution of a salt (BH+) of a weak base B:

[H3O+] = (Kw/Kb) CBH+

▪ In a buffer solution that consists of a weak acid HA and its salt MA:
[H3O+] = Ka (CHA/CMA)