Acid-Base Titrations: Instructor: Nguyen Thao Trang

Analytical Chemistry
Lecture 4
Acid-Base Titrations
Instructor: Nguyen Thao Trang

Acid-base titration
• Write balanced chemical equation between titrant and

analyte.
• Calculate composition and pH after each addition of titrant.
• Construct a graph of pH versus titrant added.
2
Titration of strong base with strong acid
• Consider titration of a strong base with a strong acid:
H+ + OH- → H2O
– The equilibrium constant: K = 1/Kw = 1/10-14 = 1014
– Reaction goes to completion
– At equivalence point (end point):
moles of titrant = moles of analyte
(V titrant)(M titrant) = (V analyte)(M analyte)
Volume, L Molar concentration, M or mol/L

3
• Consider titration of a strong base with a strong acid
3 regions of titration curve exists:
– Before the equivalence point: pH is determined by excess OH- in the

solution.
– At the equivalence point: pH is determined by dissociation of water

(H+ ≈ OH-).
– After the equivalence point: pH is determined by excess H+ in the

solution.
4
• Consider titration of a strong base with a strong acid: 50.00
mL of 0.100 M NaOH with 0.100 M HCl
First calculate the volume of HCl needed to reach the

equivalence point
(V titrant)(M titrant) = (V analyte)(M analyte)
(V HCl)(C HCl) = (V NaOH)(C NaOH)
(V HCl)(0.100 M) = (50.00 mL)(0.100 M)
à Volume HCl = 50.00 mL
5
Before the equivalence point

– Initial amount of analyte (NaOH) = 50.00 mL x 0.100 M = 5.00 mmol
– After adding 1.00 mL of HCl:
• mmol H+ added = mmol OH- consumed
• mmol H+ = (1.00 mL)(0.100 M) = 0.100 mmol
àmmol OH- remaining = 5.00 – 0.100 = 4.90 mmol
• Total volume = 50.00 mL + 1.00 mL = 51.00 mL
• [OH-] = 4.90 mmol/51.00 mL = 0.0961 M
• pOH = - log(0.0961) = 1.017 à pH = 14.000 - 1.017 = 12.983

6

– Repeat calculations for all volumes added.
– Increments can be large initially but must be reduced just before and
just after the equivalence point (around 50.00 mL in this case).
– Sudden change in pH occurs near the equivalence point.
– Greatest slope at the equivalence point.
7
At the equivalence point

– pH is determined by the dissociation of water:
H2O ↔ H+ + OH-
x x
Kw = x2 = 1.0 x 10-14
à x = 1.0 x 10-7
pH = 7.00 (at 25 oC)
8
After the equivalence point

– Excess H+ is present: After adding 51.00 mL of HCl
• Excess HCl present = 51.00 – 50.00 = 1.00 mL
• Excess H+ = (1.00 mL)(0.100 M) = 0.100 mmol
• Total volume of solution = 50.00 + 51.00 = 101.00 mL
• [H+] = 0.100 mmol/101.00 mL = 9.90 x 10-4 M
• pH = -log(9.90 x 10-4) = 3.004
9
Titration curve
Excess OH- Excess H+
Equivalence point
pH
(maximum slope or point of inflection)
7 𝑑 " 𝑝𝐻
=0
𝑑𝑉 "
50.00
Volume of HCl added (mL) 10
Titration of strong acid with strong base
• Consider titration of a strong acid with a strong base: 50.00
mL of 0.100 M HCl with 0.100 M NaOH
Titration curve
Excess H+ Excess OH-
pH
𝑑 " 𝑝𝐻
=0
𝑑𝑉 "
7
Equivalence point
(maximum slope or point
of inflection)
50.00
Volume of NaOH added (mL) 11
Weak acid-strong base
• Consider 50.00 mL of 0.0100 M acetic acid with 0.100 M
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
pKa of acetic acid = 4.76
Equilibrium constant = 1/Kb = 1/ (Kw/Ka) = 1.7 x 109 à so large, can

assume the reaction goes to completion.
Determine volume of the base at equivalence point:
mmol HC2H3O2 ≈ mmol OH-
(V NaOH)(0.100 M) = (50.00 mL)(0.0100 M)
à Volume NaOH = 5.00 mL
12
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
Before adding the base
– pH is determined by equilibrium of weak acid:
HA ↔ H+ + A-
F-x x x
[x 2 ] [x 2 ]
Ka = =
[F - x] [0.0100 - x]
x = 4.1 x 10-4
pH = 3.39
13
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
Before the equivalence point:
– By adding OH- a buffer solution of HA and A- is formed:
• After adding 0.100 mL OH-:
HA + OH- → A- + H2O
Initial mmol 0.500 0.0100 0
Final mmol 0.490 0 0.0100
⎛ [A- ] ⎞
pH = pK a + log⎜⎜ ⎟⎟
⎝ [HA] ⎠
⎛ [0.0100] ⎞
pH = 4.76 + log⎜⎜ ⎟⎟ = 3.07
⎝ [0.490] ⎠
14
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
Before the equivalence point:
– By adding OH- a buffer solution of HA and A- is formed:
• After adding 2.50 mL OH- (haft of the volume at equivalence point)
HA + OH- → A- + H2O
Initial mmol 0.500 0.250 0
Final mmol 0.250 0 0.250
⎛ [A- ] ⎞
pH = pK a + log⎜⎜ ⎟⎟
⎝ [HA] ⎠
⎛ [0.250] ⎞
pH = 4.76 + log ⎜ ⎟ = 4.76
⎝ [0.250] ⎠
15
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
At the equivalence point:
– Volume of OH- = 5.00 mL
• mmol OH- = (5.00 mL)(0.100 M) = 0.500 mmol
• HA is used up and [HA] = 0
• Only A- is present in solution à mmol A- = 0.500 mmol
• [A-] = (0.500 mmol)/(50.00 mL + 5.00 mL) = 0.00909 M (= F)
A- + H2O ↔ HA + OH-
F-x x x
[x 2 ] Kw
Kb = =
[F - x] K a 16
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
At the equivalence point:
– Volume of OH- = 5.00 mL
[x 2 ] Kw
Kb = = = 5.8 ×10−10
[F - x] K a
• x = [OH-] = 2.3 x 10-6
• pOH = 5.64 à pH = 14.00 – 5.64 = 8.36
• pH is greater than 7.00
• pH at equivalence point increases with decreasing strength of acid

17
NaOH
HC2H3O2 + OH- → C2H3O2- + H2O
After the equivalence point:
– pH is determined by the excess [OH-] (approximation)
• After adding 5.10 mL OH-
• [OH-] = (0.10 mL)(0.100 M)/(50.00 mL + 5.10 mL) = 1.81 x 10-4
• pH = 14.00 – pOH = 14.00 – 3.74 = 10.26
18
NaOH
Buffer region Excess OH-

Minimum slope
pH
8.36
pH = pKa
Equivalence point
pKa of inflection)
2.50 5.00
Volume of NaOH added (mL)
19
Weak base - strong acid
• The reverse of weak acid and strong base:
B + H+ → BH+
• Similarly assume reaction goes to completion
• Consider 50.00 mL of 0.0100 M pyridine with 0.100 M HCl(Kb

of pyridine = 1.6 x 10-9 )
– Determine volume of acid at equivalence point:
• mmol pyridine ≈ mmol H+
• (V HCl)(0.100 M) = (50.00 mL)(0.010 M)
à Volume HCl = 5.00 mL
20
Before adding the acid
– pH is determined by equilibrium of weak base (using Kb)
B + H2O ↔ BH+ + OH-
F-x x x
[x 2 ] [x 2 ]
Kb = =
[F-x] [0.0100 - x]
21
– By adding H+ a buffer solution of B and BH+ is formed:
⎛ [B] ⎞
pH = pK a + log⎜ ⎟
⎝ [BH ] ⎠
+
– When volume of H+ added = half the volume at equivalent point = 2.5

mL
pH = pKa (for BH+)
22
At the equivalence point
– Volume of H+ = 5.00 mL
• mmol H+ = (5.00 mL)(0.100 M) = 0.500 mmol
• B has been converted into BH+: B + H+ → BH+
• B is used up and [B] = 0, only BH+ is present in the solution
• pH is calculated by considering BH+
BH+ ↔ B + H+ [x 2 ] K
Ka = = w
F-x x x [F - x] K b
• x = [H+] à pH is not 7.00 but less than 7.00

23
After the equivalence point
– Strong acid (H+) is being added to weak acid (BH+)
– pH is determined by the excess [H+] (approximation)

• After adding 5.10 mL H+
• [H+] = (0.10 mL)(0.100 M)/(50.00 mL + 5.10 mL) = 1.81 x 10-4
• pH = 3.74
24
Buffer region Excess H+

Minimum slope
pKa
pH = pKa
pH
Equivalence point
of inflection)
2.50 5.00
Volume of HCl added (mL)
25
Finding the end points using pH electrodes
The end point is where the

slope of the curve is greatest:
• The end point is the volume at

which the first derivative of a
titration curve is maximum.
• The end point is the volume at

which the second derivative of a
titration curve is zero.
26
Finding the end points using indicators
• An acid-base indicator is itself an weak acid or base whose
various protonated species have different colors.
• Example: Thymol blue
– pH < 1.7: mostly red
– 1.7 < pH < 8.9: mostly yellow
– pH > 8.9: mostly blue
27
• An acid-base indicator is itself an weak acid or base whose
various protonated species have different colors.
• Acid indicator:
HIn + H2O ↔ In- + H3O+
Acid Base
• Base indicator:
In + H2O ↔ InH+ + OH-
Base Acid
• pH determines the color of the solution:
*
𝐻𝐼𝑛
𝐻( 𝑂 = 𝐾,
𝐼𝑛/
28
• Human eyes are sensitive to color change in a solution
containing a mixture of Hln and In- if:
𝐻𝐼𝑛
0.1 < / < 10
𝐼𝑛
456
– If 7 ≥ 10: the solution has the color of the pure acid (HIn)
56
456
– If 7 ≤ 0.1: the solution has the color of the pure base (In-)
56
29
• Human eyes are sensitive to color change in a solution
containing a mixture of Hln and In- if:
𝐻𝐼𝑛
0.1 < / < 10
𝐼𝑛
456
– If = 10 → 𝐻( 𝑂 * = 10 𝐾, → 𝑝𝐻 = 𝑝𝐾, - 1
567
456
– If = 0.1 → 𝐻( 𝑂 * = 0.1 𝐾, → 𝑝𝐻 = 𝑝𝐾, + 1
567
– Indicator pH range: 𝑝𝐻 = 𝑝𝐾, ± 1

– Ex. An acid indicator with pKa = 5 typically shows a complete color
change when the pH of the solution that the indicator is dissolved
changes from 4 to 6.
30
• In general:
– Acidic color if pH ≤ pKHIn – 1
– Basic color if pH ≥ pKHIn + 1
– A mixture of both colors if pKHIn - 1 ≤ pH ≤ pKHIn + 1
– Transition range: from pKHIn - 1 to pKHIn + 1
• Previous example: Thymol blue
• 1st transition range: 0.7 - 2.7

• 2nd transition range: 7.9 - 9.9
31
• Choosing an indicator:
– The difference between the observed end point (color change) and
the true equivalence point is called the indicator error .
– Use an indicator whose transition range overlaps the steepest part of
the titration curveà minimize indicator error .
Indicator Transition range (pH) acid color base color

Bromocresol
Purple 5.2 – 6.8 Yellow Purple
Bromocresol
green 3.8 – 5.4 Yellow Blue
32
33

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Analytical Chemistry

Instructor: Nguyen Thao Trang

• Write balanced chemical equation between titrant and

• Calculate composition and pH after each addition of titrant.

• Construct a graph of pH versus titrant added.

– The equilibrium constant: K = 1/Kw = 1/10-14 = 1014

– Reaction goes to completion

– At equivalence point (end point):

moles of titrant = moles of analyte

(V titrant)(M titrant) = (V analyte)(M analyte)

Volume, L Molar concentration, M or mol/L

– Before the equivalence point: pH is determined by excess OH- in the

– At the equivalence point: pH is determined by dissociation of water

– After the equivalence point: pH is determined by excess H+ in the

First calculate the volume of HCl needed to reach the

(V titrant)(M titrant) = (V analyte)(M analyte)

(V HCl)(C HCl) = (V NaOH)(C NaOH)

(V HCl)(0.100 M) = (50.00 mL)(0.100 M)

à Volume HCl = 50.00 mL

Before the equivalence point

– After adding 1.00 mL of HCl:

• mmol H+ added = mmol OH- consumed

• mmol H+ = (1.00 mL)(0.100 M) = 0.100 mmol

àmmol OH- remaining = 5.00 – 0.100 = 4.90 mmol

• Total volume = 50.00 mL + 1.00 mL = 51.00 mL

• [OH-] = 4.90 mmol/51.00 mL = 0.0961 M

• pOH = - log(0.0961) = 1.017 à pH = 14.000 - 1.017 = 12.983

Before the equivalence point

– Sudden change in pH occurs near the equivalence point.

– Greatest slope at the equivalence point.

At the equivalence point

pH = 7.00 (at 25 oC)

After the equivalence point

• Excess HCl present = 51.00 – 50.00 = 1.00 mL

• Excess H+ = (1.00 mL)(0.100 M) = 0.100 mmol

• Total volume of solution = 50.00 + 51.00 = 101.00 mL

• [H+] = 0.100 mmol/101.00 mL = 9.90 x 10-4 M

• pH = -log(9.90 x 10-4) = 3.004

(maximum slope or point of inflection)

pKa of acetic acid = 4.76

Equilibrium constant = 1/Kb = 1/ (Kw/Ka) = 1.7 x 109 à so large, can

Determine volume of the base at equivalence point:

mmol HC2H3O2 ≈ mmol OH-

(V NaOH)(0.100 M) = (50.00 mL)(0.0100 M)

à Volume NaOH = 5.00 mL

• After adding 0.100 mL OH-:

• After adding 2.50 mL OH- (haft of the volume at equivalence point)

• mmol OH- = (5.00 mL)(0.100 M) = 0.500 mmol

• HA is used up and [HA] = 0

• Only A- is present in solution à mmol A- = 0.500 mmol

• [A-] = (0.500 mmol)/(50.00 mL + 5.00 mL) = 0.00909 M (= F)

• x = [OH-] = 2.3 x 10-6

• pOH = 5.64 à pH = 14.00 – 5.64 = 8.36

• pH is greater than 7.00

• pH at equivalence point increases with decreasing strength of acid

• [OH-] = (0.10 mL)(0.100 M)/(50.00 mL + 5.10 mL) = 1.81 x 10-4

• pH = 14.00 – pOH = 14.00 – 3.74 = 10.26

Buffer region Excess OH-

• Similarly assume reaction goes to completion

• Consider 50.00 mL of 0.0100 M pyridine with 0.100 M HCl(Kb

• mmol pyridine ≈ mmol H+

• (V HCl)(0.100 M) = (50.00 mL)(0.010 M)

à Volume HCl = 5.00 mL