Chem 28 Notes (F Valera)

Acid/Base indicators have an indicator range (transition range) of approximately pKa ± 1. A

suitable indicator changes color within 1 drop of the titrant in excess of the equivalence point.
Some important acid/base indicators are given in the following table.

Indicator pKa Acid/Base Color

Methyl orange 3.46 red/orange
Bromocresol green 4.66 yellow/blue
Methyl red 5.00 red/yellow
Bromothymol blue 7.10 yellow/blue
Phenolphthalein 9.0 colorless/red

Titration curve: pH (or pOH) vs. mL of titrant; useful for determining (1) whether the titration
is feasible or not and (2) the right indicator to use

Strong Acid-Strong Base (SA-SB) Titration

e.g. 50.00 mL of 0.1000 F HCl is titrated with 0.1000 F NaOH. Calculate the pH at the
following points:
a. start of titration
b. after addition of 10.00 mL titrant
c. after addition of 50.00 mL titrant
d. after addition of 60.00 mL titrant

Solution:
• To calculate the pH before equivalence point, determine the amount of unreacted HCl
(analyte)
• To calculate the pH at equivalence point, use Kw
• To calculate the pH past equivalence point, determine the amount of excess NaOH (titrant)

Titration curve for 50.00 mL of 0.1000 F

HCl with 0.1000 F NaOH. A very steep
slope at the equivalence point region
indicates a sharp end point. The pOH is
obtained by subtracting pH from 14.00.

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 Chem 28 Notes (F Valera)

Weak Acid-Strong Base (WA-SB) Titration

e.g. 50.00 mL of a 0.1000 F HOAc (Ka = 1.8 x 10-5) is titrated with 0.1000 F NaOH. Calculate
the pH at the following points:
a. start of titration
b. after addition of 10.00 mL titrant
c. after addition of 50.00 mL titrant
d. after addition of 60.00 mL titrant

Titration curve for 50.00 mL of

0.1000 F HOAc with 0.1000 F
NaOH (curved line). The straight
lines show the change in relative
amounts of HOAc (αo) and OAc−
(α1). As αodecreases, α1 increases.
At half neutralization (25.00 mL),
αo = α1 = 0.5, and a buffer system
results. At the equivalence point, the
solution is transformed to OAc−
solution.

The titration of a weak acid with a weak base or of a weak base with a weak acid is not
feasible since the reaction does not proceed to completion, hence the end point is not sharp and
there is no suitable indicator that can be used in the titration.

For the reaction between HOAc (Ka = 1.8 x 10-5 ) and NH3 (Kb = 1.8 x 10-5-)
HOAc + NH3
NH4+ + OAc-

[ NH 4+ ][OAc − ] [ H 3O + ][OH − ] K a × K b (1.8 × 10 −5 ) (1.8 × 10 −5 )

K= × + −
= = −14
= 3.2 × 10 4
[ HOAc][ NH 3 ] [ H 3O ][OH ] Kw 1.0 × 10

Since K =3.24 x 104 << 107, then the reaction does not proceed to completion and the titration is
not feasible.
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 Chem 28 Notes (F Valera)

Effect of Concentration on Titration Curves

HCl titrated with NaOH. Curve A: 50.00 mL of

0.0500 F HCl with 0.1000 F NaOH, B: 50.00 mL of
0.000500 F HCl with 0.00100 F NaOH.
• Curve A (more concentrated solutions of
analyte and titrant) has steeper slope at the
equivalence point region than Curve B (less
concentrated solutions of analyte and titrant).
• Sharp end point for Titration A with any of the
three indicators
• Sharp end point for Titration B only with
bromothymol blue

HOAc titrated with NaOH. Curve A: 0.1000 F

HOAc with 0.1000 F NaOH. Curve B:
0.001000 F HOAc with 0.001000 F NaOH.
• Sharp end point for Curve A with
phenolphthalein
• No sharp end point for Curve B with
any indicator

Effect of Reaction Completeness on Titration Curves

The reaction completeness is determined by the values of Ka or Kb. As the value of Ka

decreases, acid strength decreases (as the value of Kb decreases, base strength decreases) and the
slope of the curve at the equivalence point region becomes less steep resulting to a limited choice
of indicator.

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 Chem 28 Notes (F Valera)

Effect of acid strength (Ka) Effect of base strength (Kb)

on titration curves on titration curves

Titration of 50.00 mL of 0.1000 F acid with Titration of 50.00 mL of 0.1000 F base with
0.1000 F base. 0.1000 F acid.

Titration of 50 mL of 0.10 F H3PO4 (triprotic acid) with 0.10 F NaOH

pKa1 = 2.15, pKa2 = 7.20, pKa3 = 12.35

A: ≅ monoprotic acid with Ka = Ka1

Region around B: H3PO4/H2PO4− buffer
system using Ka1
C (1st eq pt): NaH2PO4 soln (amphiprotic)
Region around D: H2PO4−/HPO42− buffer
system using Ka2
E (2nd eq pt): Na2HPO4 soln (amphiprotic)
Region around F: HPO42−/PO43− buffer
system using Ka3
G: Na3PO4 solution
Note that the third acid HPO42−, is too weak for possible titration

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 Chem 28 Notes (F Valera)

Titration of Mixture of Strong and Weak Acid with Strong Base

Titration curves of strong acid /weak acid mixtures with

0.1000 F NaOH. Each titration is on 25.00 mL of a solution
that is 0.1200 F in HCl and 0.0800 F in HA.

When Ka is relatively large (curves A and B), the rise in pH at the first equivalence point is small
or non-existent. Only the total number of millimoles of HCl and HA can be ascertained.

When Ka is very small, only the HCl content can be determined.

When 10−8 < Ka < 10−4, there are two useful end points. The first end point is due to the titration
of HCl. The pH is calculated from the concentration of HCl, since the amount of HA that
dissociates is negligible compared to the total concentration of HCl. Near the equivalence point,
the H3O+ that comes from the strong acid and weak acid are comparable and quadratic equation
is used to calculate for [H3O+]. After the first equivalence point, the system consists of HA and
Cl-. Since [Cl-] does not hydrolyze in aqueous solution, the system may be treated as an aqueous
solution of HA.

Titration of Alkali Mixtures

• Method Using Two Separate Titrations

o one titration uses phenolphthalein (phth) indicator (pH range = 8.0 – 9.6): Vphth is
the volume of HCl needed to reach equivalence point
o another titration uses bromocresol green (bcg) indicator (pH range = 3.8 – 5.3):
Vbcg is the volume needed to reach equivalence point; methyl orange (mo)
indicator (pH range = 3.1 – 4.4) may also be used for this titration

• Double Indicator Method

o involves a single titration using two indicators
o phenolphthalein is added at the start of titration; V1 is the volume of HCl needed
to reach the first equivalence point
o bromocresol green or methyl orange is added when phenolphthalein changes
color; V2 is the additional volume of HCl needed to reach the second equivalence
point

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 Chem 28 Notes (F Valera)

Volume Relationships in the Titration of Mixtures Containing NaOH, Na2CO3 and

NaHCO3 with HCl
Constituents in Sample VHCl for Two Separate VHCl for Double-Indicator
Titrations Method (Single Titration)
NaOH Vphth = Vbcg V1 > 0; V2 = 0
Na2CO3 Vphth = ½ Vbcg V1 = V2
NaHCO3 Vphth = 0; Vbcg >0 V1 = 0; V2 > 0
NaOH, Na2CO3 Vphth > ½ Vbcg V1 > V2
Na2CO3, NaHCO3 Vphth < ½ Vbcg V1 < V2

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 Chem 28 Notes (F Valera)

A mixture containing NaOH and NaHCO3 is not determined because they react with each other
according to the following equation: OH− + HCO3−
H2O + CO32−. The mixture becomes
NaOH and Na2CO3 if [NaOH] > [NaHCO3] or NaHCO3 and Na2CO3 if [NaHCO3] > [NaOH].

A solution contains NaHCO3, Na2CO3 and NaOH, either alone or in a permissible combination.
Titration of a 50.0-mL portion to a phenolphthalein end point requires 22.1 mL of 0.100 F HCl.
A second 50.0-mL aliquot requires 48.4 mL of the HCl when titrated to a bromocresol green end
point. Deduce the composition, and calculate the molar solute concentrations of the original
solution.

A 0.6234-g sample that might contain NaOH, Na2CO3, NaHCO3 or a permissible mixture of the
bases is titrated with o.1062 F HCl by the two-indicator method. It is found out that 40.38 mL of
the acid are required to reach the phenolphthalein end point. Methyl orange is then added to the
solution and the titration continued using an additional 12.83 mL of the acid.
(a) Identify the base or mixture of bases in the sample.
(b) Calculate the percentage of each in the sample.

Kjeldahl Method for Determining Organic Nitrogen

Sample (bound nitrogen)

conc’d H2SO4
∆
NH4+
cool, dilute
add NaOH

NH3 liberated

distilled into excess strong acid

excess acid is back-titrated with standard base

The ammonia from a 1.325-g sample of fertilizer is distilled into 50.00-mL of 0.2030 N H2SO4,
and 25.32 mL of 0.1980 N NaOH is required for back-titration. Calculate the percentage of
nitrogen in the sample.

Since most proteins contain approximately the same percentage of nitrogen, multiplication of
this percentage by a suitable factor gives the percentage protein in a sample:
6.25 for meats
6.38 for dairy products
5.70 for cereals