Module 9a Buffer Preparation and Hydrolysis of Salts Concept
Module 9a Buffer Preparation and Hydrolysis of Salts Concept
I. INTRODUCTION
Salts or ionic compounds are product of neutralisation reactions between an acid and a base. Take sodium nitrite (NaNO2)
for instance.
NaOH (base) upon reacting with HNO2 (acid) forms the salt NaNO2. Under certain conditions, the ions of a salt may react
with water to generate H+ and OH– ions. This reaction is called hydrolysis. Consequently, the resulting pH of the solution
may not be only neutral but may also be acidic or basic. This behavior of cations and anions as acids or bases depends on
the strength of acid or base they are associated with.
Buffers are solutions that resist drastic pH change. The components of a buffer solution neutralize an acid or a base
introduced into a solution. Buffers are important, especially in biological systems.
In this module, you will learn about the pH of salt solutions and hydrolysis reactions, as well as the preparation of buffer
solutions. Knowledge and familiarity of the names and chemical formula of the various strong and weak acids and bases
would prove to be useful.
For now, all salts that you will be dealing with are strong electrolytes. This means that when they are dissolved in water,
cations and anions are fully liberated (indicated by the “→” arrow). When a salt is dissolved in water, there are four possible
cases to consider when determining its acidity or basicity.
When salts of a strong acid and a strong base are dissolved in water, the resulting pH of the solution is neutral. For instance,
when sodium nitrate (NaNO3), a salt formed by the reaction between NaOH and HNO3 (a strong base and strong acid,
respectively), dissolves in water, it dissociates completely:
H2 O -
NaNO3(s) → Na+
(aq) + NO3(aq) (Rxn 9a-2)
None of the ions has affinity for proton (H+) or can produce one. Thus, these are termed as spectator ions as no hydrolysis
are expected from both of them. Thus, the pH of the solution is neutral.
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More examples: NaCl, CaCl2, KI
Considering a salt in which its cation is derived from a strong base while its anion is a conjugate base of a weak acid, when
dissolved in water, the pH would be basic. For instance, when sodium acetate (NaCH3COO) is dissolved in water, it would
dissociate into Na+ ion and CH3COO– ion.
H2 O -
NaCH3 COO(s) → Na+
(aq) + CH3 COO(aq) (Rxn 9a-3)
Sodium ion, the spectator ion, has neither acid nor base properties. However, the acetate ion (CH3COO-), the conjugate
base of a weak acid CH3COOH has affinity to a proton. Since the best proton available in the solution is water, it would
react with it to yield CH3COOH, thus, producing OH–. The generation of OH- renders the solution basic.
- -
CH3 COO(aq) + H2 O(l) ⇌ CH3 COOH(aq) + OH(aq) (Rxn 9a-4)
NOTE: The hydrolysis reaction (Rxn 9a-4) is reversible, as denoted by the “⇌" arrow.
On the other hand, a solution of salt in which the anion is derived from a strong acid while the cation is the conjugate acid
of a weak base is acidic. Considering ammonium chloride (NH4Cl) when dissolved in water, the dissolution is given by the
reaction below.
H2 O -
NH4 Cl(s) → NH+
4(aq) + Cl(aq) (Rxn 9a-5)
Since the anion Cl– is derived from a strong acid HCl, it is a spectator ion and would not affect the pH. However, the
presence of NH4+ would lead to production of H3O+, since it is the conjugate acid of the weak base NH3. The generation of
H3O+ renders the solution acidic.
+
NH+
4(aq) + H2 O(l) ⇌ NH3(aq) + H3 O(aq) (Rxn 9a-6)
For this case, the cation component of the salt is a conjugate acid of a weak base, while the anion component is the
conjugate base of a weak acid. Both cation and anion are capable of hydrolysis. To predict the pH, the relative strengths
of the cation acting as acid and anion acting as base should be considered. In other words, the Ka of the cation and Kb of
the anion must be compared. The rules summarized in Table 9a-1 would be the reference for the prediction of the resulting
pH.
Table 9a-1. Predicting the pH of a Salt Solution when the Cation and Anion are Hydrolysable.
Condition pH Explanation
Ka (cation) > Kb (anion) Acidic The hydrolysis of the cation would proceed in greater extent
compared to the hydrolysis of the anion. Since there would be
more H+ generated compared to OH-, the solution will be acidic.
Ka (cation) < Kb (anion) Basic The resulting solution will be basic since hydrolysis of the anion
will be of greater extent compared to that of the cation.
Ka (cation) ≈ Kb (anion) Nearly neutral If Ka of the cation and Kb of the anion are not significantly
different, then the solution will be nearly neutral.
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Sample Problem 1: Given the following salts, determine the ion/s which will undergo hydrolysis for each. Also provide the
spectator ion/s, hydrolysis reaction/s if applicable, and most probable pH of the resulting solution.
a. KNO3
Dissolution: H2 O -
KNO3(s) → K+ (aq) + NO3(aq)
Note: Do not forget to include the state of the chemical species.
Hydrolysable ion/s: none (K+ is derived from KOH, NO3- is derived from HNO3)
Spectator ion/s: K+, NO3- (both ions do not undergo hydrolysis)
Hydrolysis reaction: none
Most probably pH: neutral
b. KCN
Dissolution: H2 O -
KCN(s) → K+ (aq) + CN(aq)
Hydrolysable ion/s: CN- (it is the conjugate base of the weak acid HCN)
Spectator ion/s: K+ (it is derived from the strong base KOH)
- -
Hydrolysis reaction: CN(aq) + H2 O(l) ⇌ HCN(aq) + OH(aq)
(CN- acts as a base and accepts a proton from H2O)
Most probably pH: basic
c. NH4NO3
Dissolution: H2 O -
NH4 NO3(s) → NH+
4(aq) + NO3(aq)
Hydrolysable ion/s: NH4+ (it is the conjugate acid of the weak base NH3)
Spectator ion/s: NO3- (it is derived from the strong acid HNO3)
+
Hydrolysis reaction: NH+
4(aq) + H2 O(l) ⇌ NH3(aq) + H3 O(aq)
(NH4+ acts as an acid and donates a proton to H2O)
Most probably pH: acidic
d. NH4CN
Dissolution: H2 O -
NH4 CN(s) → NH+
4(aq) + CN(aq)
Hydrolysable ion/s: NH4+, CN- (NH4+ is the conjugate acid of the weak base NH3, CN- is the conjugate
base of the weak acid HCN)
Spectator ion/s: none
+
Hydrolysis reaction: NH+4(aq) + H2 O(l) ⇌ NH3(aq) + H3 O(aq)
(NH4+ acts as an acid and donates a proton to H2O)
- -
CN(aq) + H2 O(l) ⇌ HCN(aq) + OH(aq)
(CN- acts as a base and accepts a proton from H2O)
Most probably pH: Ka (NH4+) = 5.6 × 10-10
Kb (CN-) = 1.6 × 10-5
Since Ka (NH4+) < Kb (CN-), the solution is basic.
SAQ 1. Predict the most probable pH of the aqueous solution of the following salts.
1. Na2SO4
2. C5H5NHClO4
Thus far, you are only able to predict the most probable pH of a salt solution through a qualitative approach. Now, you will
perform some calculations involving hydrolysis reactions.
Sample Problem 2: Calculate the pH of a 0.25 M NaF solution. The Ka value for HF is 7.2 × 10-4.
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Step 2: Write the hydrolysis reaction (if there are any).
Na+ is from the strong base NaOH, so it will not hydrolyze. F-, on the other hand, is hydrolysable because it is the conjugate
base of the weak acid HF. F- acts as a base and accepts a proton from H2O.
-
F-(aq) + H2 O(l) ⇌ HF(aq) + OH(aq) (Rxn 9a-8)
Due to the formation of OH-, it can already be predicted that the pH will be basic.
For the ICE table, let x = amount of F- that will undergo hydrolysis.
-
F-(aq) + H2 O(l) ⇌ HF(aq) + OH(aq)
I 0.25 M - 0 0
C -x - +x +x
E 0.25 M - x - x x
-14
Kw 1.0 ×10 -11
Kb = = = 1.38889 × 10
Ka 7.2 ×10
-4
Note: Do not round off anything yet. Just add extra digits.
We are solving for concentrations, so a negative value would have no physical meaning. Thus, x1 will be used as the “x”.
Calculate pOH first, but do not round off yet. Just take note of the number of significant figures. Also remember to take
into account the rules for significant figures for logarithm.
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Finally, for the pH:
Therefore, the pH of 0.25 M NaF solution is 8.27. As predicted from the hydrolysis reaction in Rxn 9a-8, the solution is
basic, and this is consistent with the calculated pH.
First, you must show that the abovementioned condition holds true. For this example:
c 0.25 M 10
= = 1.8 × 10
K 1.38889 × 10
-11
x2 x2 -11
≈ = 1.38889 × 10
0.25 - x 0.25
In this approximation, you are essentially assuming that the x in the denominator is approximately zero. This greatly
simplifies the calculation, and you no longer need to use the quadratic formula to solve for x. Using this approximation, x
= 1.863390727 × 10-6, which is very close to the x value obtained by the longer method.
Sample Problem 3: Determine whether an aqueous solution of NH4F will be acidic, basic or neutral given that the Ka and Kb
of HF and NH3 are 7.2 x 10-4 and 1.8 x 10-5, respectively.
-14
Kw 1.0 ×10 -10
Ka, NH+ = = ≈ 5.6 × 10
4 Kb, NH3 1.8 ×10
-5
-14
Kw 1.0 ×10 -11
Kb, F- = = ≈ 1.4 × 10
Ka, HF 7.2 ×10
-4
Since Ka, NH+ > Kb, F- , the hydrolysis of NH4+ will proceed to a greater extent compared to the hydrolysis of F-. Therefore,
4
the resulting solution will be acidic.
Note: For this problem, it is alright to not take note of the significant figures because it only involves comparing the
magnitude of Ka and Kb.
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SAQ 2.
1. Calculate the pH of a 0.15 M NH4Cl solution.
2. Will an aqueous solution of CH3NH3CN be acidic, basic, or neutral? Support you answer with calculations. (Ka
-10 -4
(HCN) = 6.2 × 10 ; Kb (CH3NH2) = 4.4 × 10 )
IV. BUFFERS
Buffers are solutions that resist drastic pH change upon addition of small amount of acid or base. They contain both acidic
and basic components that can neutralize OH- and H3O+ ions, respectively.
A buffer solution must contain an acid-base conjugate pair. Thus, buffers are prepared by mixing a solution containing: a)
a weak acid + its conjugate base or b) a weak base + its conjugate acid. The pH of a buffer system can be adjusted by
changing the base-to-acid ratio.
How does a buffer solution resist drastic pH change? Consider the CH3COOH – NaCH3COO buffer system. It is composed of
the weak acid component, acetic acid (CH3COOH), and the conjugate base component in salt form, sodium acetate
(NaCH3COO). The net ionic equation describing the acetic acid buffer system can be written as:
Since H3O+ was generated, we expect that this buffer is slightly acidic upon preparation.
Now, upon addition of a base (OH-) to the buffer system, the acid component will neutralize it.
Upon addition of an acid (H3O+) to the buffer system, the base component will neutralize it.
A buffer system will only work if the pH of interest is within the useful buffering range:
A. HENDERSON-HASSELBALCH EQUATION
The Henderson – Hasselbalch equation is the main equation used in preparing buffer solutions. To derive it, consider the
dissociation of a general weak monoprotic acid HA (Rxn 9a-13), as well as its Ka expression (Eqn 9a-4).
+
HA(aq) + H2 O(l) ⇌ A-(aq) + H3 O(aq) (Rxn 9a-13)
[A- ][H3 O+ ]
Ka = (Eqn 9a-4)
[HA]
Take the negative logarithm of Eqn 9a-4, and apply the properties of logarithms.
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[A- ][H3 O+ ]
- log Ka = - log
[HA]
+ [A- ]
- log Ka = - log[H3 O ] - log
[HA]
Now, apply the definition of pKa and pH to arrive at the Henderson – Hasselbalch equation (Eqn 9a-5).
[A- ]
pKa = pH - log
[HA]
[A- ]
pH = pKa + log (Eqn 9a-5)
[HA]
V. BUFFER PREPARATION
Buffer solutions can be prepared in multiple ways. In this discussion, two ways of preparing buffers will be discussed: A)
from stock buffer solution, and B) from pure, dry, weighable solids.
Sample Problem 4: Describe how you will prepare 1.00 L of 0.100 M carbonate buffer at pH 9.80 using 0.500 M stock
solution with pH of also 9.80.
To solve this problem, simply calculate for the volume of the stock solution needed (V1) using Eqn 9a-6.
C1V1 = C2V2
C2 V2 (0.100 M)(1.00 L)
V1 = = = 0.200 L = 200 mL
C1 (0.500 M)
Thus, V1 = 200 mL. Take note that V1 has three significant figures. However, this is not yet the final answer since you are
asked to DESCRIBE.
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Final answer: To prepare the buffer, transfer 200 mL of the 0.500 M stock buffer solution into a 1.00 L volumetric flask,
and then dilute to mark using distilled water.
The calculations involved in preparing a buffer solution from pure, dry, weighable solids are better discussed by going
straight to an example.
Sample Problem 5: Describe how you will prepare 1.00 L of 0.100 M carbonate buffer at pH 9.80 using any two appropriate
reagents given below:
For carbonic acid (H2CO3), Ka1 = 4.45 × 10-7 and Ka2 = 4.69 × 10-11.
To solve this problem, the first thing to do is to select the appropriate solids. Carbonic acid is a diprotic acid (it can donate
two protons), hence the two Ka values. For NaHCO3 (s) and Na2CO3 (s), the sodium cation (Na+) is just a spectator ion. Focus
on the anions: HCO3- and CO32-, respectively.
Now, to select the appropriate solids, apply the useful buffering range as shown in Eqn 9a-2.
To prepare the buffer system, the acid component must have HCO3- and the base component must have CO32-. This is
because the desired pH of 9.80 is within the range 9.33-11.33. Therefore, the appropriate solids are NaHCO3 and Na2CO3.
The appropriate solids have been selected, and their respective masses can now be calculated.
Step 1: Calculate the base – to – acid mole ratio using the Henderson – Hasselbalch equation (Eqn 9a-5).
2-
[CO3 ]
pH = pKa2 + log
[HCO-3 ]
2-
[CO3 ]
log = pH-pKa2
[HCO-3 ]
2-
[CO3 ] pH-pKa2
= 10
[HCO-3 ]
2-
[CO3 ] 9.80-10.33
= 10
[HCO-3 ]
2-
[CO3 ]
= 0.2951209227
[HCO-3 ]
Note: pKa2 = 10.33 was used because this is the pKa for HCO3- ⇌ CO32-. Do not round off yet.
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Step 2: Calculate the mole fraction of each component.
By definition, the mole fraction of a component is calculated as:
2- 2-
[CO3 ] 0.2951209227 mol CO3
= 0.2951209227 =
[HCO-3 ] -
1 mol HCO3
Hence,
- 2-
total no. of moles = 1 mol HCO3 + 0.2951209227 mol CO3 = 1.2951209227 mol
So,
2-
2- 0.2951209227 mol CO3
mol fraction of CO3 = = 0.2278713266
1.2951209227 mol
-
- 1 mol HCO3
mol fraction of HCO3 = = 0.7721286734
1.2951209227 mol
Note: The mole fraction is unitless. The sum of the mole fractions must be equal to 1.
mol g
mass of Na2 CO3 = (0.100 ) (1.00 L) (105.99 ) (0.2278713266) ≈ 2.42 g Na2 CO3
L mol
mol g
mass of NaHCO3 = (0.100 ) (1.00 L) (84.008 ) (0.7721286734) ≈ 6.49 g NaHCO3
L mol
Note: Masses will have 3 significant figures. The calculated values are not yet the final answer because you are asked to
describe.
Final answer: To prepare the buffer, weigh 2.42 g Na2CO3 and 6.49 g NaHCO3, dissolve in minimum amount of distilled
water, transfer quantitatively to a 1.00 L volumetric flask, and dilute to mark with distilled water.
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VI. ANSWERS TO SAQs
SAQ 1 SAQ 3
1. Neutral 1. Not a buffer
2. Acidic 2. Buffer
3. Buffer
4. Buffer
SAQ 2 SAQ 4
1. 5.04 1. V stock buffer solution = 6.25 mL
-11 2. 3.68 g NaHCO3, 0.230 mL H2CO3
2. Ka, CH + = 2.3 × 10
3 NH3
-5
Kb, CN- = 1.6 × 10
Basic
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Link Used
Wikimedia Commons. (2006). File:Volumetric flask hg.jpg. Retrieved December 30, 2020 from
https://commons.wikimedia.org/wiki/File:Volumetric_flask_hg.jpg
SUGGESTED LINKS
These supplementary videos might help you further understand the topic:
Khan Academy. (2014, August 15). Acid-base properties of salts [Video]. Khan Academy.
https://www.khanacademy.org/science/ap-chemistry/acids-and-bases-ap/acid-base-equilibria-tutorial-ap/v/acid-base-
properties-of-salts
Khan Academy. (2014, August 16). pH of salt solutions [Video]. Khan Academy.
https://www.khanacademy.org/science/ap-chemistry/acids-and-bases-ap/acid-base-equilibria-tutorial-ap/v/ph-of-salt-
solutions
Khan Academy. (2016, March 14). pH and pKa relationship for buffers [Video]. Khan Academy.
https://www.khanacademy.org/science/ap-chemistry/buffers-titrations-solubility-equilibria-ap/buffer-solutions-tutorial-
ap/v/ph-and-pka-relationship-for-buffers
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