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Acid-Base Properties of Salt Solutions

• We know, with NO doubt that:

Hydrolysis and Buffers – HCl, HNO3, H2SO4, HCIO4, HF, etc. are ACIDIC.
– NaOH, KOH. Ca(OH)2, etc. are BASIC.

• Ions can also be acidic or basic. (right?)

– since when salts are dissolved in water they
dissociate into ions, salts can also be acidic or
basic.

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Reaction of Anion with Water Reaction of Anion with Water

• Anions are generally basic. • Anion (X-) can be considered as conjugate

base of Acid (HX)
• Hence, they can react with water in a – e.g. Cl- is CB of HCl, CH3COO- is CB of CH3COOH
hydrolysis reaction to form OH- and the
conjugate acid: • Remember!
a) CBs of strong acids are insignificant bases
X- (aq) + H2O (l) HX (aq) + OH- (aq) b) CBs of weak acids are weak bases
c) CBs of insignificant acids are strong bases

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Reaction of Cation with Water Reaction of Cation with Water

• Generally, cations are acidic. • Cation (HX+) can be considered as conjugate

acid of base (X)
• Hence, they can react with water in a – e.g. NH4+ is CA of NH3, H3O+ is CA of water
hydrolysis reaction to form H+ and the
conjugate base: • Remember!
a) CAs of strong bases are insignificant acids
HX+ (aq) + H2O (l) X (aq) + H3O+ (aq) b) CAs of weak bases are weak acids
c) CAs of insignificant bases are strong acids

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Reaction of Cation with Water Reaction of Cation with Water

• Metal cations are also • Attraction between

nonbonding electrons
acidic (Lewis acids) on oxygen and the
metal causes a shift of
the electron density in
• Most metal cations water.
that are hydrated in • This makes the O-H
solution also lower bond more polar and
the water more acidic.
the pH of the solution
• Greater charge and
smaller size make a
cation more acidic.

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Effect of Salt Solutions on pH Effect of Salt Solutions on pH

a) An anion that is the d) Cations of the strong

conjugate base of a Arrhenius bases will
strong acid will not not affect the pH.
affect the pH. e) Other metal ions will
b) An anion that is the cause a decrease in pH.
conjugate base of a f) When a solution
weak acid will increase contains both the
the pH. conjugate base of a
c) A cation that is the weak acid and the
conjugate acid of a conjugate acid of a
weak base will decrease weak base, the affect on
the pH. pH depends on the Ka
and Kb values.
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Calculating pH: Acidic Salts Calculating pH: Basic Salts

pH = -log √CsaltKa pOH = -log √CsaltKb

pH = -log √Csalt(Kw/Kb) pOH = -log √Csalt(Kw/Ka)

Since usually, Kb is Since usually, Ka is
given for the base given for the acid

• NOTE: only true if Csalt/Ka > 1000. • NOTE: only true if Csalt/Kb > 1000.

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Calculating pH Examples
1) 1.02 M NH4Cl

2) 2.13 M CH3COONa
If conditions are NOT
met, use equilibrium, 3) 5.07 M KCl

and quadratic equation 4) 4.12 M NaF

5) 0.08 M NH4Cl

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Common-Ion effect Common-Ion effect

• Suppose we have a solution of the weak acid • The common-ion is the F-.
hydrofluoric acid (Ka= 7.2 x10-4), and its salt sodium • by virtue of Le Châtelier’s principle:
fluoride (NaF).

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Common-Ion effect Buffered Solutions

• The common-ion effect is quite general for • Buffered solutions contain

acids and bases with their corresponding weak conjugate acid-base
conjugate ions. pair.

• They are able to resist

• E.g. drastic changes in pH upon
–CH3COOH and CH3COO- the addition of small
–NH3 and NH4+ amounts of strong acids
and bases.
• NOTE: the effect is significant only for weak acids and bases.

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Composition of Buffered Solutions Action of Buffered Solutions

• A buffer resists changes in pH because it has:

– an acid that neutralized added OH- ions
– basic component neutralizes H+ ions.

• E.g.
–CH3COOH (acid) + CH3COONa (base)
–HF (acid) and NaF (base)
–NH3 (base) and NH4Cl (acid)
If a small amount of OH- is added to a solution with
equal concentrations of HF and NaF, the HF reacts with
the OH− to make F− and water.
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Action of Buffered Solutions Calculations involving Buffers

• Consider the dissociation of an acid HA

HA (aq) ⇋ H3O+ (aq) + A- (aq)

• The Ka expression for this is:

[H3O+] [A−]
Ka =
[HA]
If a small amount of H+ is added to a solution with equal
concentrations of HF and NaF, the F- reacts with the H+
to make HF and water.
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Calculations involving Buffers Henderson–Hasselbalch Equation

• By simple rearrangement we get: • FINALLY:

[A−] [base]
Ka = [H3 O+] pKa = pH − log
[HA] [acid]
• Taking the –log from both sides, it becomes:
• For acidic buffers:
[A−]
−log Ka = −log [H3O+] + −log [base]
[HA] pH = pKa + log
[acid]

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Henderson–Hasselbalch Equation Addition of Strong Acid and Bases to buffers

• For basic buffers:

[acid]
pOH = pKb + log
[base]

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Adding Strong Acid to a Buffered Solution Adding Strong Base to a Buffered Solution

• For acidic buffers: • For acidic buffers:

[base-nacid] [base+nbase]
pH = pKa + log pH = pKa + log
[acid+nacid] [acid-nbase]

• For basic buffers: • For basic buffers:

[acid+nacid] [acid-nbase]
pOH = pKb + log pOH = pKb + log
[base-nacid] [base+nbase]

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Henderson–Hasselbalch Equation Addition of strong acid to buffers

• Example: A buffered solution contains • What will be the final pH if 2 mL 6.0 M HCl is
0.25 M NH3 (Kb = 1.8 x10-5) and 0.40 M added to 1L of:
NH4Cl. Calculate the pH of this solution.
[0.40 M NH4+] 1. 0.25 M NH3
pOH = -log (1.8 x10-5) + log 2. Buffer described in previous example.
[0.25 M NH3]
pOH = 4.7447 + 0.20411
pOH = 4.95
pH = 9.05

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Addition of strong base to buffers
• What will be the final pH if 2 mL 6.0 M NaOH
is added to:
1. 0.25 M NH3
2. Buffer described in previous example.
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Buffer Capacity
• Greater concentration of both of acid and
base components, greater buffer capacity.
• If ratio is the same, pH range stays the same.
• 10 M NH3:10 M NH4+ higher buffer capacity
than 1 M NH3 : 1 M NH4+, but same pH range.
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pH range of Buffer solutions
• The pH range is the range of pH values over
which a buffer system works effectively.
• It is best to choose an acid with a pKa close to
the desired pH.
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Sources:
• Chemistry: The Central Science, 11th edition. Theodore L.
Brown, H. Eugene LeMay, Jr., and Bruce E. Bursten. , McGraw-
Hill, Philippines, 2004
• General Chemistry: Principles and Modern Applications, 1Oth
Edition. Ralph H. Petrucci, F. Geoffrey Herring, Jeffry D.
Madura, and Carey Bissonnette. Philippines, 2002
• Chemistry, 7th edition. Steven S. Zumdahl , Susan A. Zumdahl ,
Houghton Mifflin Co., 2002
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