Module 5a – Neutralization Titration

Introduction Hence, the indicator exhibits its acid color when

https://www.youtube.com/watch?v=d1XTOsnNlgg&list=WL&in
dex=2

https://www.youtube.com/watch?v=wAeRb0CEaWQ&list=WL& and the indicator exhibits its base color when

index=10

Standard Solutions:

Strong acids/Strong bases Substituting the two ratios in Eqn 2,

– because they react more completely with an analyte Full acid color: [H3O+] = 10 Ka
and provide sharper end points.
– Common acid standard solutions: dilute HCl, HClO4 or Full base color: [H3O+] = 0.1 Ka
H2SO4 Taking the logarithm of both sides,
– HNO3 is seldom used because its oxidizing properties
offer potential for undesirable side reactions. pH (acid color) = -log (10 Ka) = pKa + 1
– Common base standard solutions: NaOH, KOH, and pH (base color) = -log (0.1 Ka) = pKa - 1
occasionally Ba(OH)2.
Therefore, the indicator pH range = pKa ± 1
Indicators:
- are weak organic acids or a weak organic bases whose Exercise 1: Derive a similar relationship for the basic-type
indicator.
undissociated form differs in color from its conjugate
Base-type indicator:
form.
base conjugate acid
Acid-type indicator: In + H2 O ⇌ InH+ + OH-
base color acid color
acid conjugate base
HIn + H2O ⇌ In- + H3O+ Meaning of “the indicator pH range = pKa ± 1”:
acid color base color
If the acid dissociation constant, Ka, of an acid indicator is 1.0 x
Ka for the dissociation of an acid-type indicator:
10-5 (pKa = 5), its color change is evident when the pH of the its
[H3 O+][In− ] surrounding solution is from 4 to 6. So, the indicator should have
Ka = [HIn]
(1)
pKa or pKb close to the pH of the equivalence point because its
Rearranging the Ka gives color transition range will be mostly likely evident to that pH at
Ka[HIn] equivalence-point region. Please watch the video below.
[H3 O+ ] = (2)
[In−] https://www.youtube.com/watch?v=1YlXtpF-
According to Eqn. 2: 19A&list=WL&index=9&t=18s
1. Ka is relatively constant. It will not change. The Common Acid/Base Indicators
2. H3O+, HIn, In- are variables. Their values are dependent
to each other.
3. The concentration of H3O+ determines the [HIn]/[In-] (in
plane words, the ratio of the acid to its conjugate form )
4. [HIn]/[In-], in turn, controls the color of the solution
5. This color-changing capacity makes the indicator
suitable for detecting the endpoint of acid-base
titration.

In the presence of more acid, the color of the solution is that of

the acid color. This eventually changes into the base color upon
addition of more base, when the presence of conjugate form
increases.

The color changes is detected by the human eye at a limited

range; this is when [HIn]/[In-] is approximately 10 to 0.1.
 2. Random error
limited ability of the eye (visual uncertainty = ±0.5 to
±1 pH unit) to distinguish the intermediate color of the
indicator.
dependent on the:
1. pH change per milliliter of reagent at the
equivalence point;
2. concentration of the indicator; and
3. sensitivity of eye to the two indicator colors.
the visual uncertainty can be decreased by matching
the color of the titrated solution to that of a reference
standard containing a similar amount of indicator at
the appropriate pH.

Titration of a Strong Acid with a Strong Base

For the solution of strong acid, the two sources of H3O+:

1. reaction of acid with water, HA + H2O ⇌ H3O+ + A-
2. dissociation of water, 2 H2O ⇌ H3O+ + -OH
Mass-balance equation: [H3O+] = CHA + [-OH] ≈ CHA
Similarly, the analogous relationship applies for the two sources
of -OH in a solution of a strong base:
[-OH] = CB + [H3O+] ≈ CB

Calculating the Titration Curve of Strong acid with Strong base

Three (3) stages in titration:

1. pre-equivalence
compute the [acid] from: (a) CHA and (b) amount
of base added then get the pH
2. equivalence
the [H3O+] and [-OH] are equal, pH = 7.00
3. post-equivalence
compute the CB of the excess base, calculate the
pOH then the pH. Remember, pH + pOH = 14.00.
➢ https://www.youtube.com/watch?v=JoGQYSTlOKo&list=W
L&index=8&t=20s
➢ https://www.youtube.com/watch?v=HO1dsNrzE58&list=W
L&index=7&t=97s
Variables that Influence the Behavior of Indicators:
1. temperature Example 1: Generate the hypothetical titration curve for the
2. ionic strength of the medium titration of 50.00-mL 0.0500 M HCl with 0.1000 NaOH. Assume
3. presence of organic solvents that all solution is only diluted with pure water.
4. colloidal particles Initial point:
can cause the transition range to shift by 1 or more
pH units. pH = - log [CHCl] = - log 0.0500 = 1.30

Titration Errors with Acid/Base Indicators Pre-equivalence point:

1. Systematic error What is the new pH of the solution when 10 mL of the titrant is
added?
- the pH at which the indicator changes color differs
from the pH at the equivalence point.
- can be minimized by choosing the indicator carefully
or by making blank correction.
Equivalence point:
At equivalence point, the no. mmol HCl = no. mmol NaOH. The
[H3O+] is from the dissociation of water. Therefore,
The change in pH in the equivalence-point region is large
with higher concentration.

Titrating a Strong Base with a Strong Acid

Post-equivalence point:
What is the new pH of the solution when 25.10 mL of the titrant
is added?
At post-equivalence point, the titrant is in excess. Therefore,
Exercise 3: Assume that all solution is diluted with pure water.
Generate a hypothetical titration curve of 50.00-mL 0.05000 M
NaOH with 0.1000 M HCl. Supply the pH of the sample solution
when added with the following volumes of titrant:

Volume of 0.1000 M HCl pH of 50.00-mL 0.0500 M NAOH

0.00 ?
10.00 ?
20.00 ?
24.00 ?
24.90 ?
25.00 ?
25.10 ?
26.00 ?
30.00 ?
Titration Curve

Exercise 2: Show the pH calculation process when 0.00, 10.00,

Buffer
20.00, 24.00, 24.90, 25.90, 30.00 mL of 0.100 M NaOH are
- is a mixture of a weak acid and its conjugate base or a
added to 50.00-mL 0.0500 M HCl.
weak base and its conjugate acid that resists changes in pH
of a solution.
Effect of Concentration in the Equivalence-Point Region

Mass-balance equations:
[HA] + [H3O+] = CHA + [-OH]
[HA] = CHA - [H3O+] + [-OH]
[A-] + [-OH] = CNaA + [H3O+]
[A-] = CNaA + [H3O+] - [-OH]
[H3O+] and [-OH] are usually so small relative to CHA and CNaA, so 0.170 M
pH = - log (5.70 x 10-10) + log = 9.11
0.230 M
[HA] ≈ CHA and [A-] ≈ CNaA
and the pH change is 9.11 – 9.07 = 0.04
The Ka expression becomes,
[H3 O+ ] = K a
CHA (b) Upon addition of HCl, the base, NH3, neutralizes the
Eqn 2
CNaA
effect of the added H3O+:
Taking the logarithm of both sides,
C
- log [H3O+] = - log Ka - log C HA
NaA
CNaA
pH = pKa + log Eqn 3
CHA

This equation is called Henderson-Hasselbalch equation.

0.150 M
Example 2: What is the pH of a solution that is 0.400 M in formic pH = - log (5.70 x 10-10) + log 0.250 M = 9.02
acid and 1.00 M in sodium formate? Ka for formic acid = 1.80 x
and the pH change is 9.02 – 9.07 = - 0.05
10-4.
HCOOH + H2O ⇌ H3O+ + HCOO- Ka = 1.80 x 10-4 Exercise 4: What weight of sodium formate (NaHCOO, 68.008
Kw g/mol) must be added to 400.0 mL of 1.00 M formic acid
HCOO- + H2O ⇌ HCOOH + -OH Kb = = 5.56 x 10-11 (HCOOH) to produce a buffer solution that has a pH of 3.50? Ka
Ka

[HCOOH] ≈ CHA = 0.400 M; [HCOO-] ≈ CNaA = 1.00 M for formic acid = 1.80 x 10-4.

CNaA
Use: pH = pKa + log CHA Titrating Weak Acids or Weak Base
-4 1.00 M
pH = - log (1.80 x 10 ) + log = 4.14
0.400 M Four (4) different types of calculations:
Example 3: Calculate the pH of a solution that is 0.200 M in NH 3 At initial point, the solution contains only a weak acid or a
and 0.300 M in NH4Cl. The dissociation constant Ka for NH4+ is weak base, calculate [H3O+] or [-OH], then pOH and pH.
5.70 x 10-10. [H3 O+ ][A−]
For weak acid: HA + H2O ⇌ H3O+ + A- Ka = [HA]
NH4+ + H2O ⇌ NH3 + H3O+ Ka = 5.70 x 10-10 Ka =
[x][x]
; [𝐇𝟑 𝐎+ ] = x = √K a CHA
[HA]
Kw [BH+ ][OH− ]
NH3 + H2O ⇌ NH4+ + -OH Kb = = 1.75 x 10-5 For weak base: B + H2O ⇌ BH+ + -OH Kb =
Ka [B]
CNaA 0.200 M [x][x]
pH = pKa + log = - log (5.70 x 10-10) + log 0.300 M = 9.07 Kb = ; [𝐎𝐇− ] = x = √K b CB
CHA [B]
After various increments of titrant have been added, the
solution consists of a series of buffers. Calculate pH = pKa +
Effect of Dilution to pH CNaA
log like in Example 2, 3 and 4.
CHA
pH of a buffer remains essentially independent of dilution
At the equivalence point, the solution contains only the
as long as [H3O+] and [-OH] remain small relative to CHA and
conjugate base if a weak acid is being titrated; and conjugate
CNaA
acid if a weak base is being titrated. Calculate pH using
Example 4: Effect of Added Acids and Bases to pH For conjugate base: [𝐎𝐇− ] = x = √K b CA−
For conjugate acid: [𝐇𝟑 𝐎+] = x = √K a CBH+
Calculate the pH change that takes place when a 100-mL
Beyond the equivalence point, the pH is governed largely by
portion of (a) 0.0500 M NaOH and (b) 0.0500 M HCl is added
the concentration of the excess titrant which is either a strong
to 400 mL of the buffer solution that was described in
acid or a strong base.
Example 3.
https://www.youtube.com/watch?v=x3CbfUr449Y&list=WL
(a) Upon addition of NaOH, the acid, NH4+, of the buffer
&index=3
neutralizes the effect of the added -OH:
https://www.youtube.com/watch?v=WbDL7xN-
NH4+ + -OH ⇌ NH3 + H2O
The analytical concentrations of NH₃ and NH₄Cl then Pn0&list=WL&index=5
become https://www.youtube.com/watch?v=pmHlKhv7C0E&list=WL
&index=2&t=6s
https://www.youtube.com/watch?v=kWucfgOkCIQ&list=WL
&index=4&t=2s
Example 5: Titrating Weak Acid with Strong Base [-OH] ≈ CNaOH = (55.00)(0.1000 M)−(50.00 mL)(0.100 M)
(50.00+55.00) mL
= 4.762 × 10−3 M

Generate a curve for the titration of 50.00-mL 0.1000 M acetic pH = 14.00 – {- log (5.34 x 10-6 + 4.762 x 10-3)} = 11.67
acid with 0.1000 M NaOH. Ka for acetic acid = 1.75x10-5
Titration curve:
pH at Initial point:
+
[𝐇𝟑 𝐎 ] = x = √Ka CHA = √(1.75 × 10−5 )(0.100) = 1.32 × 10−3
pH = - log (1.32 x 10-3) = 2.88

pH after increments of the titrant (Ex. 5-mL NaOH):

Upon addition of NaOH, the acetic acid (HA) neutralizes the

effect of the added -OH:
HA + NaOH ⇌ NaA + H2O
(50.00 mL)(0.100 M) − (5.00 mL)(0.100 M)
CHA = = 0.08182 M Volume of 0.1000 M pH of 50.00 mL of 0.1000 M
(50.00 + 5.00) mL
NaOH, mL Acetic acid with 0.1000 M NaOH
The solution also contains conjugate base, sodium acetate (NaA) 0.00 2.88
which is calculated from the added titrant: 5.00 3.80
10.00 ?
(5.00 mL)(0.100 M)
CNaA = = 9.091 × 10−3 M 25.00 4.76
(50.00 + 5.00) mL
40.00 ?
CNaA 9.091 ×10−3 M
pH = pKa + log = - log (1.75 x 10-5) + log = 3.80 49.00 ?
CHA 0.08182 M
49.90 ?
pH after increments of the titrant (Ex. 25-mL NaOH): 50.00 8.73
50.10 10.02
HA + NaOH ⇌ NaA + H2O 51.00 ?
(50.00 mL)(0.100 M) − (25.00 mL)(0.100 M) 55.00 11.67
CHA = = 0.03333 M
(50.00 + 25.00) mL 60.00 ?
The solution also contains conjugate base, sodium acetate (NaA): Exercise 5: Show the calculation processes of the pH missing
(25.00 mL)(0.100 M)
from the table above.
CNaA = = 0.03333 M
(50.00 + 25.00) mL Exercise 6: What volume of 2.00 M NaOH must be added to
CNaA 0.03333 M
pH = pKa + log = - log (1.75 x 10-5) + log 0.03333 M = 4.76 300.00 mL of 1.00 M glycolic acid to produce a buffer solution
CHA
having a pH of 4.00? Ka for glycolic acid = 1.47 x 10-4.
pH at equivalence point:

At equivalence point no. of mol of acid = no. of mol of base which Example 6: Titrating Weak Base
requires 50.00 mL of 0.100 M NaOH. All HA is converted to NaA
which is the only component in the solution. Generate a curve for the titration of 50.00-mL 0.05000 M NaCN
with 0.1000 M HCl. Ka for HCN = 6.2 x 10-10
(50.00 mL)(0.100 M)
CNaA = = 0.05000 M [H3 O+][CN−]
(50.00 + 50.00) mL HCN + H2O ⇌ H3O+ + CN- Ka = [HCN]
= 6.2 × 10−10
K
For conjugate base: [OH− ] = √K b CA− = √ Kw CNaA [HCN][OH−] 𝐾𝑤
a CN- + H2O ⇌ HCN + -OH Kb = [CN− ]
= = 1.61 × 10−5
𝐾𝑎
1.00 ×10−14
= √ 1.75 ×10−5 (0.0500 M) = 5.345 × 10−6 M
pH at Initial point:
pH = 14.00 – (- log 5.34 x 10-6) = 8.73
[𝐎𝐇− ] = x = √K b CCN− = √(1.61 × 10−5 )(0.0500) = 8.972 × 10−4
pH beyond the equivalence point: pH = 14.00 – {- log (8.972 x 10-4)} = 10.95
Ex. after addition of 50.10-mL NaOH, the solution contains 5.34 x pH after increments of the titrant (Ex. 5-mL HCl):
10-6 –OH from the conjugate base and
Upon addition of HCl, the CN- (B) neutralizes the effect of the
[-OH] ≈ CNaOH = (50.10)(0.1000 M)−(50.00 mL)(0.100 M)
(50.00+50.10) mL
= 9.990 × 10−5 M added H3O+:
pH = 14.00 – {- log (5.34 x 10-6 + 9.990 x 10-5)} = 10.02 B + H3O+ ⇌ BH+ + H2O
(50.00 mL)(0.0500 M) − (5.00 mL)(0.100 M)
CB = = 0.03636 M
After addition of 55.00-mL NaOH, the solution contains 5.34 x 10- (50.00 + 5.00) mL
6–
OH from the conjugate base and
The solution also contains conjugate acid, HCN (BH+): Prepared by:
(5.00 mL)(0.100 M)
CBH+ = = 9.091 × 10−3 M
(50.00 + 5.00) mL Mary-Ann A. Landiao, RCh, MSc
CB 0.03636 M
pH = pKa + log C -10
= - log (6.2 x 10 ) + log 9.091 ×10−3 M = 9.81 Faculty, Chemistry Dept.
BH+

pH at equivalence point:

At equivalence point no. of mol of acid = no. of mol of base which

requires 25.00 mL of 0.100 M HCl. All B is converted to BH+ which
is the only solute in the solution.
(25.00 mL)(0.100 M)
CBH+ = = 0.03333 M
(50.00 + 25.00) mL
For conjugate acid: [H3 O+ ] = √K a CBH+
= √(6.2 × 10−10 )(0.03333 M) = 2.066 × 10−6 M
pH = - log 2.066 x 10-6 = 5.68

pH beyond the equivalence point:

Ex. after addition of 25.10-mL HCl, the solution contains 2.066 x

10-6 H3O+ from the conjugate acid and

[H3O+] ≈ CHCN = (25.10)(0.1000 M)−(50.00 mL)(0.0500 M)

(50.00+25.10) mL
= 1.332 × 10−4 M

pH = - log (2.066 x 10-6 + 1.332 x 10-4) = 3.87

Titration curve:

volume of 0.1000 pH of 50.00 mL of 0.05000 M

M HCl, mL NaCN with 0.1000 M HCl
0.00 10.95
5.00 9.81
10.00 ?
15.00 ?
20.00 ?
24.10 ?
24.90 ?
25.00 5.68
25.10 3.87
25.90 ?
30.00 ?
Exercise 7: Show the calculation process of the pH missing from
the table above.
Exercise 8: What volume of 0.200 M HCl must be added to 250.0
mL of 0.300 M sodium mandelate to produce a buffer solution
with a pH of 3.37? Ka for madelic acid = 4.00 x 10-4.