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Chapter 2: Volumetric methods

Part 1: Overview of Titrimetry
• Principle
Physical and chemical methods • Types of titrimetric methods
for food analysis 1 • Law of equivalence (Định luật đương lượng)
• Requirements of chemical reactions
By: Dương Hữu Huy
• Titration strategies

Principle • Equivalence point: The point in a titration where stoichiometrically

• Titrimetry refers to a group of methods of quantitative
analysis in which an analyte is determined basing on its
stoichiometric reaction with a reagent of established
concentration introduced to a sample gradually until
the analyte is consumed quantitatively.
• Reaction: R + X → products
equivalent amounts of analyte and titrant react.
• End point: The point in a titration where we stop adding titrant.
• Indicator: A colored compound whose change in color signals the end
R point of a titration.
• Titration error: The determinate error in a titration due to the
difference between the end point and the equivalence point.

• Analyte (X): unknown concentration X

• Standard (R): known concentration, also called as
titrant
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Types of titrimetric methods Law of equivalence

• At equivalence point:
• Acid – base titrations
VR* CR = VX* CX
NaOH + HCl → NaCl + H2O
• Precipitation titrations R (VR; CR) • CR and CX in normality
Ag⁺ + Cl⁻ → AgCl↓ • For example:
• Complexometric titrations + Standard NaOH (R): 9.7 mL and 0.1 N
Ca²⁺ + H2Y²⁻ → CaY²⁻ + 2H⁺ + Analyte HCl (X): 10 mL and CHCl = ? N
• Redox titrations X (VX; CX) + CNaOH*VNaOH = CHCl*VHCl
I³⁻ + 2S2O3²⁻ → S4O6²⁻ + 3I⁻
=> VHCl = 0.1*9.7/10 = 0.097 N

Requirements of chemical reactions Titration strategies

1. Analyte stoichiometrically reacts with titrant 1. Direct titration

2. Rapid reaction 2. Back titration

3. Selectivity 3. Displacement titration

4. Suitable indicator is available to find end point with an acceptable How to calculate the result?

level of accuracy
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Chapter 2: Volumetric methods

Part 2: Acid – base titration Definition
• Definition Brønsted–Lowry acid–base theory
• Acid – base strength • Acid: donate proton (proton donor) => conjugate base
• Balance equations
• Base: accept proton (proton acceptor) => conjugate acid
• pH of monoprotic strong acid (or base)
• Example:
• pH of monoprotic weak acid (or base)
• pH of conjugate acid-base pair HCl + NaOH → NaCl + H2O
• pH of polyprotic weak acid HCl: acid and Cl⁻: conjugate base
• pH of salt solutions NaOH: base and H2O: conjugate acid

• Conjugate acid–base pair: Acid – base strength

1. A conjugate acid is formed when a proton is added to a base,
2. and a conjugate base is formed when a proton is removed from an acid.
• Example: HCl/Cl⁻; CH3COOH/CH3COO⁻
• Relative strengths of acids and bases:
1. The stronger an acid, the weaker its conjugate base,
2. and, conversely, the stronger a base, the weaker its conjugate acid.
• Example: HCl is strong acid and Cl⁻ is weak conjugate base
• Strong acid: completely transfer their protons. E.g.: HCl, H2SO4 …(Ka~∞)
• Weak acid: partially donate their protons => Ka: acid dissociation constant.
E.g.: CH3COOH, HCOOH…
• Strong base: for the most common, completely dissociates to produce the
hydroxide ion. E.g.: NaOH, KOH … (Kb~∞)
• Weak base: partially accept protons => Kb: base dissociation constant. E.g.:
NH3…
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Acid dissociation constant - Ka Base dissociation constant - Kb

• The equilibrium constant for a reaction in which an acid donates a • The equilibrium constant for a reaction in which a base accepts a
proton to the solvent (Ka) proton from the solvent (Kb).
• HA + H2O H3O⁺ + A⁻ • B + H2 O BH⁺ + OH⁻
⁺ [ ⁻]
•𝐾 = • 𝐾𝑏 =
⁺[ ⁻]
[ ]
[ ]
• pKa = -logKa • pKb = -logKb
• E.g.: CH3COOH : Ka = 1.74*10⁻⁵ and pKa = 4.76
• E.g.: NH3: Kb = 1.8*10⁻⁵ and pKb =
HCN : Ka = 6.2*10⁻¹⁰ and pKa = 9.21
Which acid is stronger?

Relationship of Ka and Kb Balance equations

Ka.Kb = Kw = 10⁻¹⁴
pKa + pKb = 14
• E.g. 1: Kb of CH3OO⁻ is 5.71*10⁻¹⁰. Calculate Ka of CH3COOH.
• E.g. 2: Ka of NH4⁺ is 5.7*10⁻¹⁰. Calculate Kb of NH3.
• Mass balance equation: An equation stating that matter is conserved,
and that the total amount of a species added to a solution must equal
the sum of the amount of each of its possible forms present in solution.
• Charge balance equation: An equation stating that the total
concentration of positive charge in a solution must equal the total
concentration of negative charge.
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Example 1: Example 2:

• Write mass and charge balance equations of 0.1 M HCl solution?

• Solution:
HCl → H⁺ + Cl⁻
H2O H⁺ + OH⁻
Mass balance equation: 0.1 = [Cl⁻]
Charge balance equation: [H⁺] = [Cl⁻] + [OH⁻]

pH of monoprotic strong acid pH of monoprotic strong base

• Strong acids: HCl, HBr, HI, HNO3, HClO4, H2SO4 (exception)… • Strong bases: NaOH, KOH …
• HA: Ca (M) => [H⁺] is estimated as: • Solution of B: Cb (M) => [OH⁻] is estimated as:
[H+]2 - Ca [H+] - Kw = 0 (*) • Approximately: [OH⁻] = Cb => pOH = -logCb => pH = 14 – pOH
• Approximately (Ca > 10⁻⁶ M): [H⁺] = Ca => pH = -logCa • E.g.: Calculate pH of 0.01 M NaOH solution?
• E.g.: Calculate pH of 0.01 M HCl solution? => [OH⁻] = Cb = 0.01 M => pOH = -log[OH⁻] = 2 => pH = 14 – 2 = 12
=> [H⁺] = Ca = 0.01 M => pH = -log[H⁺] = 2
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pH of monoprotic weak acid pH of monoprotic weak base

• Weak acid: CH3COOH, HCN … • Weak base: NH3 …

• HA: Ca (M) and Ka => [H⁺] is estimated as: • B: Cb (M) and Kb => [OH⁻] is estimated as:
• Approximately (Ca >> [H⁺] and [H⁺] >> [OH⁻]): • Approximately:
• E.g.: The Kb value for NH3 is 1.8*10⁻⁵. Calculate pH of 0.01 M NH3
• E.g.: The Ka value for CH3COOH is 1.8*10⁻⁵. Calculate the pH of a solution?
0.01 M CH3COOH solution.
=> [OH⁻] = 𝐾𝑏𝐶𝑏 = 1.8 ∗ 10 ∗ 0.01 = 0.0004243 M
=> [H⁺]= 𝐾𝑎𝐶𝑎 = 1.8 ∗ 10 ∗ 0.01 = 0.0004243 M
=> pOH = 3.4 => pH = 14 – 3.4 = 10.6
=> pH = -log[H⁺] = 3.4

• E.g. 1: The Ka value of CH3COOH is 1.8*10⁻⁵. Calculate the pH of

pH of conjugate acid-base pair solution 0.2 M CH3COOH and 0.05 M CH3COONa?
• Solution:
• Conjugate acid-base pair: CH3COOH/CH3COO⁻; NH4⁺/NH3 … This is buffer solution. Ca = 0.2 M, Cb = 0.05 M and Ka = 1.8*10⁻⁵ (pKa
=> buffer solution = 4.75)
=> pH = pKa + log (Cb/Ca) = 4.75 + log(0.05/0.2) = 4.15
• Solution of HA/A⁻: HA (Ca, Ka) and A⁻ (Cb):
• E.g. 2: The Kb value of NH3 is 1.8*10⁻⁵. Calculate the pH of solution
0.1 M NH4⁺ and 0.25 M NH3.
• Solution:

• Approximately:
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pH of polyprotic weak acid pH of salt solution

• Polyprotic weak acid: H2S, H2CO3, H3PO4….
• Diprotic acid H2A: Ca, Ka1 and Ka2 => [H⁺] is estimated as:
[H+]4 + Ka1[H+]3 + (Ka1Ka2 – Ka1Ca – KH2O)[H+]2 – (KH2OKa1 +
2Ka1Ka2Ca)[H+] - KH2OKa1 Ka2 = 0
• Approximately: [H⁺] = 𝐾𝑎1𝐶𝑎
• E.g.: The pKa1 and pKa2 values of H2S are 7 and 13. Calculate the pH of
0.05 M H2S solution?
Due to pKa1 >> pKa2 => [H⁺] = 𝐾𝑎1𝐶𝑎 = 10 ∗ 0.05 => pH = 4.15
1. Strong acid + strong base. E.g.: NaCl …=> pH = 7
2. Strong acid + weak base. E.g.: NH4Cl …=> monoprotic weak acid
of NH4⁺
3. Weak acid + strong base: E.g.: CH3COONa …=> monoprotic weak
base of CH3COO⁻
4. Polyprotic acid + strong base: E.g.: Na2CO3, Na3PO4 …=>
polyprotic weak base of anions
5. Amphiprotic solution: E.g.: NaHCO3 …=> pH = ½ (pKa1 + pKa2)

Chapter 2: Volumetric methods

Part 2: Acid – base titration (cont) Principle

• Principle • Based on acid-base reaction

R
• pH indicator E.g.: NaOH + HCl = NaCl + H2O
• Standard solution • During titration, [H⁺] and [OH⁻] of solution change
• Titration of strong acid and strong base (vice versa) => pH change

• Titration of weak acid and strong base (vice versa) • End point is determined by pH indicator (visual X
method)
• Result calculation: Va*Ca = Vb*Cb
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pH indicators Indicator’s color transition region

• Finding the end point with visual indicator. HIn  H+ + In– (*)

• Organic dyes and weak acid or base. acid color baz color

• Acid specie and it’s conjugate base are different color.

• Color of indicator depends on pH of solution.
E.g.: phenolphthalein
• Symbols: HIn or InOH ∆pH = pH range = 2
 pT value: is pH value with clear
change of color in pH range.

Titration curve

• Relationship of [H⁺] or pH and volume of titrant (acid or base

standard)
• Titration curve shows the change of pH during titrating
• Used to choose an suitable indicator.
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Characterization of titration curve

• Equivalence point coincides to inflection point of curve.

• A broad change of pH value around equivalence point is observed
pHeq
even only small amount of titrant was added
• A broad change of pH (khoảng bước nhảy pH): for approximately,
0.1% in excess of analyte before equivalence point and 0.1% in
excess of titrant after equivalence point. (0.99 < F < 1.01)

E.g.: Titration of 100 mL of 0.1 M HCl with 0.1 M NaOH. Find a broad change of pH?
(assuming 0.99 < F < 1.01) E.g.: Titration of 50 mL of 0.1 M NaOH with 0.1 M CH3COOH. Find a
Solution:
broad change of pH? (assuming 0.99 < F < 1.01)
• Reaction: HCl + NaOH = NaCl + H2O
• At equivalence point: NaCl solution => pHeq = 7
• 0.1% in excess of HCl before equivalence point (F=0.99): pH0.99 = ?
V of solution = 100 + 99.9 = 199.9 mL
Number of mole of HCl residue: n = 0.1%*0.1*0.1 = 10⁻⁵ (mol)
=> [H⁺] = n/V = 10⁻⁵/0.1999 = 5* 10⁻⁵ => pH = -log[H⁺] = 4.3
• 0.1% in excess of NaOH after equivalence point (F=1.01): pH1.01 = ?
V of solution = 100 + 100.1 = 200.1 mL
Number of mole of NaOH excess: n = 0.1%*0.1*0.1 = 10⁻⁵ (mol)
=> [OH⁻] = n/V = 10⁻⁵/0.2001 = 5* 10⁻⁵ => pOH = -log[OH⁻] = 4.3 => pH = 9.7
• pH values change from 4.3 to 9.7 with only 0.2 mL of NaOH is added.
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Note for a broad pH change

• A broad pH change is as large as possible

• A broad pH change depends on:
1. Concentration of acid and base
2. Strength of acid and base

Selection of pH indicator

• pH indicator range is within a broad change of pH value.

• pT value is closed to pHeq as possible.
E.g.: pH indicator range of several indicators are: phenolphthalein (8.3 –
10.0), Tashiro (5.2 – 5.6); Thymol blue (8.0 – 9.0); Methyl red (4.4 – 6.2).
Choose correct indicator for two below titrations:
1. Titration of 100 mL of 0.1 M HCl with 0.1 M NaOH. A broad change of
pH is 4.3 – 9.7.
2. Titration of 50 mL of 0.1 M NaOH with 0.1 M CH3COOH. A broad
change of pH is 7.73 – 10.
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Practices: Which indicator is appropriate? Standard solutions

• Acid standard solution: HCl and H2SO4 …

• Acid stock standard solution: H2C2O4.2H2O …
• Base standard solution: NaOH and KOH …
• Base stock standard solution: Na2B4O7.10H2O ..
Always standardizing a TITRANT if it is not stock standard before use.

Titration of strong acid and strong base

Titration of 10 mL of 0.1 M HCl with
0.1 M NaOH. Construct a titration
curve? NaOH C, V (0.1M; ?)
Solution:
• At eq: C*V = Co*Vo => V = 10 mL
• Before adding NaOH (V =0): 0.1 M
HCl C0, V0 (0.1M; 10mL)
HCl
=> pH = -log[H⁺] = 1
• 50% NaOH added (V = 5 mL):
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Titration of strong acid and strong base Titration of strong acid and strong base

• After adding 50% NaOH (V = 5 mL): ?M HCl solution • At eq, adding 100% NaOH (V = 10 mL): NaCl solution
=> pHeq = 7
nHCl residue = nHCl initial – nNaOH added = (10*0.1 – 5*0.1)/1000 = 5*10⁻⁴ mol
• After adding 101% NaOH (V = 10.1 mL): ?M NaOH solution
Vtotal = 10 + 5 = 15 mL = 0.015 L nNaOH excess = nNaOH added – nHCl initial = (10.1*0.1 – 10*0.1)/1000 = 10⁻⁵ mol
=> [H⁺] = n/V = 5*10⁻⁴/0.015 = 0.0333 M => pH = 1.48 Vtotal = 10.1 + 10 = 20.1 mL = 0.0201 L
• After adding 99% NaOH (V = 9.9 mL): ?M HCl solution => [OH⁻] = n/V = 10⁻⁵/0.0201 = 0.0004975 => pOH = 3.3 => pH = 10.7
• Atter adding 150% NaOH (V = 15 mL): ?M NaOH solution
nHCl residue = nHCl initial – nNaOH added = (10*0.1 – 9.9*0.1)/1000 = 10⁻⁵ mol
nNaOH excess = nNaOH added – nHCl initial = (15*0.1 – 10*0.1)/1000 = 5*10⁻⁴ mol
Vtotal = 10 + 9.9 = 19.9 mL = 0.0199 L Vtotal = 15 + 10 = 25 mL = 0.025 L
=> [H⁺] = n/V = 10⁻⁵/0.0199 = 0.0005025 M => pH = 3.3 => [OH⁻] = n/V = 5*10⁻⁴ /0.025 = 0.02 => pOH = 1.7 => pH = 12.3

Titration of strong acid and strong base Titration of strong acid and strong base
Titration curve
14.0
VNaOH (mL) F pH Summary
0 0 1
12.0
5 0.5 1.5
9 0.9 2.3 10.0 1. pHeq = 7
9.5 0.95 2.6 Phenolphthalein
Equivalence point
9.9 0.99 3.3 8.0 2. A broad pH change: 3.3 – 10.7
Bromophenol blue
pH

9.99 0.999 4.3

6.0 3. Indicator: phenolphthalein, methyl red, bromophenol blue
10 1 7.0
10.01 1.001 9.7 4.0 4. Standard: NaOH 0.1 M
10.1 1.01 10.7
10.5 1.05 11.4 2.0 5. Analyte: HCl
11 1.1 11.7
0.0
15 1.5 12.3
0 5 10 15 20
VNaOH (mL)
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Titration of strong acid and strong base Titration of weak acid and strong base

Procedure Titration of weak acid and strong base

Step 1: Add 0.1 M NaOH to burette Titration of 50 mL of 0.02 M

CH3COOH (pKa = 4.75) with 0.1 M
Step 2: In each of 3 erlenmeyer flask, precisely take 10.00 mL of HCl NaOH. Construct a titration curve?
NaOH C, V (0.1M; ?)
with unknown concentration and add several drops of indicator (e.g. PP) Solution:
• At eq: C*V = Co*Vo => V = 10 mL
Step 3: Titrate with NaOH until color change (e.g. pink) • Before adding NaOH (V =0): 0.02 M
Step 4: Calculate concentration of HCl using: CH3COOH (weak acid) CH3COOH C0, V0 (0.02M;
=> [H⁺] = 𝐾𝑎𝐶𝑎 = 10 . ∗ 0.02 = 50mL)
VHCl*CHCl = VNaOH*CNaOH 0.0006
=> pH = -log[H⁺] = 3.22

Titration of weak acid and strong base Titration of weak acid and strong base

• Denote: a = CH3COOH, b = CH3COONa, and c = NaOH • After adding 99% NaOH (V = 9.9 mL): ?M CH3COOH and
• After adding 50% NaOH (V = 5 mL): ?M CH3COOH and CH3COONa solution => buffer solution
CH3COONa solution => buffer solution
na residue = na initial – nc added = (50*0.02 – 9.9*0.1)/1000 = 0.00001 mol
na residue = na initial – nc added = (50*0.02 – 5*0.1)/1000 = 0.0005 mol
nb produced = nc added = 5*0.1/1000 = 0.0005 mol nb produced = nc added = 9.9*0.1/1000 = 0.00099 mol
Vtotal = 50 + 5 = 55 mL = 0.055 L Vtotal = 50 + 9.9 = 59.9 mL = 0.0599 L
Ca = n/V = 0.0005 /0.055 = 0.0091 M Ca = n/V = 0.00001/0.0599 = 0.000167 M
Cb = n/V = 0.0005 /0.055 = 0.0091 M
Cb = n/V = 0.00099 /0.0599 = 0.0165 M
=> pH = pKa + log(Cb/Ca) = 4.75
=> pH = pKa + log(Cb/Ca) = 6.74
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Titration of weak acid and strong base Titration of weak acid and strong base

• At eq, adding 100% NaOH (V = 10 mL): ?M CH3COONa => weak • After adding 101% NaOH (V = 10.1 mL): ?M NaOH solution
base nc residue = nc added – na initial = (10.1*0.1 – 50*0.02)/1000 = 0.00001 mol
nb produced = nc added = (10*0.1)/1000 = 0.001 mol
Vtotal = 50 + 10.1 = 0.0601 L
Vtotal = 50 + 10 = 0.06 L
Cb = n/V = 0.001/0.06 = 0.0167 M C = n/V = 0.00001/0.0601 = 0.000166 M = [OH⁻]
pKa = 4.75 => pKb = 9.25 => pOH = 3.78 => pH = 10.22
=> [OH⁻]= 𝐾𝑏𝐶𝑏 = 10 . ∗ 0.0167 = 3.1*10-6 • Atter adding 150% NaOH (V = 15 mL): ?M NaOH solution
=> pOH = 5.5 => pH = 8.5 nc residue = nc added – na initial = (15*0.1 – 50*0.02)/1000 = 0.0005 mol
Vtotal = 50 + 15 = 0.065 L
C = n/V = 0.0005/0.065 = 0.0077 M = [OH⁻]
=> pOH = 2.11 => pH = 11.9

Titration of weak acid and strong base Titration of strong acid and strong base

14 Summary
VNaOH pH
12
0 3.22
5 4.76 10 1. pHeq = 8.5
9 5.71 8 2. A broad pH change: 6.8 – 10.2
9.9 6.76
pH

10 8.50 6 3. Indicator: phenolphthalein

10.1 10.22 4
4. Standard: NaOH 0.1 M
11 11.21 2
15 11.89 5. Analyte: CH3COOH
0
0 5 10 15 20
VNaOH, ml
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Titration of strong acid and strong base

Procedure Application

Step 1: Add 0.1 M NaOH to burette • Standardizing a titrant

Step 2: In each of 3 erlenmeyer flask, precisely take 50.00 mL of • Acid content in food
CH3COOH with unknown concentration and add several drops of • Protein content by Kjeldahl method
indicator (e.g. PP)
•…
Step 3: Titrate with NaOH until color change (e.g. pink)
Step 4: Calculate concentration of CH3COOH using:
VCH3COOH*CCH3COOH = VNaOH*CNaOH

Exercise 1: Titration of 50.0 mL of 0.100 M HCl with 0.200 M NaOH.

Construct a titration curve, and find suitable indicator and explain why?
Exercise 2: Titration of 50.0 mL of 0.100 M acetic acid, CH3COOH
(pKa = 4.75), with 0.100 M NaOH. Construct a titration curve, and find
suitable indicator and explain why?
Exercise 3: Titration of 50.0 mL of 0.100 M ammonia, NH3 (pKb =
4.76) with 0.100 M HCl. Construct a titration curve, and find suitable
indicator and explain why?