Analytical

Chemistry II
UNIT 1: PRINCIPLES OF NEUTRALIZATION
TITRATIONS
❖ Neutralization titrations are widely used to determine the amounts of
acids and bases and to monitor the progress of reactions that produce or
consume hydrogen ions.

❖ Standard solutions of strong acids and strong bases are used extensively
for determining analytes that are themselves acids or bases or analytes
that can be converted to such species.

❖ This chapter explores the principles of acid/base titrations. In addition,

we investigate titration curves that are plots of pH vs. volume of titrant,
and present several examples of pH calculations.

2
 Types Of Acid/Base Titrations
❖Like all titrations, neutralization titrations depend on a chemical
reaction of the analyte with a standard reagent.

❖Titration of a strong ❖Titration of a weak ❖Titration of a weak

acid with a strong base acid with a strong base base with a strong acids
❖Hydrochloric or sulfuric ❖Acetic or lactic acid with ❖Sodium cyanide or
acid with sodium sodium hydroxide sodium salicylate with
hydroxide hydrochloric acid
❖Titrimetry includes a group of analytical methods based on
determining the quantity of a reagent of known concentration that is
required to react completely with the analyte.

❖Volumetric titrimetry is a type of titrimetry in which the

standard reagent is measured volumetrically.

❖Coulometric titrimetry is a type of titrimetry in which the

quantity of charge in coulombs required to complete a reaction with
the analyte is measured.
 Defining Some Terms
❖A standard solution is a reagent of known concentration
that is used in a titrimetric analysis.

❖ Titration is a process in which a standard reagent is added

to a solution of an analyte until the reaction between the
analyte and reagent is judged to be complete.
 Defining Some Terms
❖Back-titration is a process in which the excess of a standard
solution used to consume an analyte is determined by titration
with a second standard solution.
❖Back-titrations are often required when the rate of reaction
between the analyte and reagent is slow or when the standard
solution lacks stability.
Equivalence Points & End Points
❖The equivalence point of a titration cannot be determined
experimentally.
❖The equivalence point is the point in a titration when the
amount of added standard reagent is equivalent to the amount
of analyte.
❖The end point is the point in a titration when a physical
change occurs that is associated with the condition of chemical
equivalence.
Equivalence Points & End Points
❖Indicators are often added to the analyte solution to give an
observable physical change (the end point) at or near the
equivalence point.

❖The difference in volume or mass between the equivalence

point and the end point is the titration error.
 Primary Standards
❖A primary standard is a highly purified compound that serves as
a reference material in all volumetric and mass titrimetric methods.

❖Important requirements for a primary standard are:

1. High purity (established methods for confirming purity should be
available)

2. Atmospheric stability
 Primary Standards
3. Absence of hydrate water so that the composition of the solid does
not change with variations in relative humidity

4. Ready availability at modest cost

5. Reasonable solubility in the titration medium

6. Reasonably large molar mass so that the relative error associated

with weighing the standard is minimized
 Secondary Standards
❖A secondary standard is a compound whose purity has been
established by chemical analysis and that serves as the reference material
for a titrimetric method of analysis.

❖Desirable Properties of Standard Solutions

1. Be sufficiently stable so that it is only necessary to determine its
concentration once.
2. React rapidly with the analyte so that the time required between
additions of reagent is minimized
 Secondary Standards
3. React completely with the analyte so that satisfactory end
points are realized

4. Undergo a selective reaction with the analyte that can be

described by a balanced equation
 Establishing the Concentration of
Standard Solutions
The direct method in which a carefully weighed quantity of a primary
standard is dissolved in a suitable solvent and diluted to a known volume
in a volumetric flask.
The second method is by standardization (indirect method) in
which the titrant to be standardized is used to titrate
(1) a weighed quantity of a primary standard,

(2) a weighed quantity of a secondary standard,

(3) a measured volume of another standard solution.

 Treating Titration Data
Titration curves are plots of a concentration-related variable as a
function of reagent volume.

The two most widely used end points involve :

❖(1) changes in color due to the reagent, the analyte, or an indicator and
❖(2) a change in potential of an electrode that responds to the
concentration of the reagent or the analyte.
 Types of Titration Curves
Sigmoidal curve

important observations are

confined to a small region
(typically ± 0.1 to ± 0.5 mL)
surrounding the equivalence
point.
 Types of Titration Curves
Linear segment curve
measurements are made on
both sides of - but well away
from - the equivalence point.
Measurements near
equivalence are avoided.
 Titration curves of pH and pOH versus volume of base
for the titration of 0.1000 M HCl with 0.1000 M NaOH.

Strong acid titrated

with a strong base
 Standard Solutions
The standard solutions used in neutralization titrations are strong
acids or strong bases because these substances react more
completely with an analyte than do weak acids and bases, and as a
result, they produce sharper end points.

Standard solutions of bases are usually prepared from solid sodium,

potassium, and occasionally barium hydroxides. Again, always use
eye protection when handling dilute solutions of these reagents.
 Standard Solutions
Standard solutions of acids are prepared by diluting concentrated
hydrochloric, perchloric, or sulfuric acid.

Nitric acid is seldom used because its oxidizing properties offer the
potential for undesirable side reactions.

Hot concentrated perchloric and sulfuric acids are potent oxidizing

agents and are very hazardous. Fortunately, cold dilute solutions of
these reagents are safe to use in the analytical laboratory without
any special precautions other than eye protection
 Acid/Base Indicators
An acid/base indicator is a weak organic acid or a weak organic base
whose undissociated form differs in color from its conjugate form.

Phenolphthalein
 Acid/Base Indicators
For example, the behavior of an acid-type indicator, HIn, is
described by the equilibrium

In this reaction, internal structural changes accompany dissociation

and cause the color change. The equilibrium for a base-type
indicator, In, is
 Acid/Base Indicators
The equilibrium-constant expression
for the dissociation of an acid-type
indicator takes the form
We see then that the hydronium ion
is proportional to the ratio of the
concentration of the acid form to the
concentration of the base form of the
indicator, which in turn controls the
color of the solution.
 Acid/Base Indicators
The human eye is not very sensitive to color differences in a
solution containing a mixture of HIn and In-, particularly when the
ratio [HIn]/[In-] is greater than about 10 or smaller than about 0.1.

Because of this restriction, the color change detected by an average

observer occurs within a limited range of concentration ratios from
about 10 to about 0.1
 Acid/Base Indicators
HIn exhibits its pure acid
color when

and its base color when

 Acid/Base Indicators
the range of hydronium To obtain the indicator pH range, we take the
ion concentrations needed negative logarithms of the two expressions:
for the indicator to change
color can be estimated:
pH(acid color) = -log(10 Ka)
For full acid color:
= pKa + 1
[ H3O+] = 10 Ka
pH(basic color) =- log(0.1 Ka)
For the full base color:
= pKa - 1
[H3O+] = 0.1 Ka

indicator pH range = pKa ±1

 Acid/Base Indicators
What Variables Influence the Behavior of Indicators?
The pH interval over which a given indicator exhibits a color
change is influenced by temperature, by the ionic strength of
the medium, and by the presence of organic solvents and
colloidal particles.

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The list of
acid/base
indicators is
large and
includes a
number of
organic
compounds.
 Titrations Of Strong Acids and Strong
Bases
The hydronium ions in an aqueous solution of a strong acid have
two sources:
(1) the reaction of the acid with water and
HA + H2O → H3O+ + A–
(2) the dissociation of water itself
H2O → OH– + H3O+

We create this relationship: [H3O+] = CHA + [OH–]

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 Titrations Of Strong Acids and
Strong Bases
In all but the most dilute solutions, however, the contribution from the
strong acid far exceeds that from the solvent. Thus, for a solution of HCl
with a concentration greater than about 10-6 M, we can write:
[H3O+] = cHCl + [OH-] = cHCl

where [OH-] represents the contribution of hydronium ions from the

dissociation of water. An analogous relationship applies for a solution
of a strong base, such as sodium hydroxide. That is
[OH-] = cNaOH + [H3O+] =cNaOH
 Titrations Of Strong Acids and
Strong Bases
Three types of calculations must be done in order to construct the
hypothetical curve for titrating a solution of a strong acid with a strong
base

Each calculation corresponds to a distinct stage in the titration:

(1) Pre equivalence,

(2) equivalence, and

(3) post equivalence.

 Titrations Of Strong Acids and
Strong Bases
Before the equivalence point, we calculate the pH from the molar
concentration of unreacted acid. From cHA or cHCl

At the equivalence point, the solution is neutral and pH=7.00.

Beyond the equivalence point, we first calculate pOH and then pH.
Remember that pH= pKw – pOH

At 25oC pH = 14.00 - pOH.

 Example 1-1
Generate the hypothetical titration curve for the titration
of 50.00 mL of 0.0500 M HCl with 0.1000 M NaOH at 25oC.
Initial Point
Before any base is added, the solution is 0.0500 M in H3O+

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After Addition of 10.00 mL of Reagent
The hydronium ion concentration is decreased as a result of both reaction
with the base and dilution. So, the remaining HCl concentration, cHCl is

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After Addition of 10.00 mL of Reagent
And since [H3O+] = cHCl
After Addition of 25.00 mL of Reagent: The Equivalence Point
At the equivalence point, neither HCl nor NaOH is in excess, and so, the
concentrations of hydronium and hydroxide ions must be equal.
The only source of hydronium ions are from water.
Substituting this equality into the ion-product constant for water yields

7-35
After Addition of 25.10 mL of Reagent
The solution now contains an excess of NaOH

7-36
Additional values beyond the equivalence point are calculated in the same way.
The results of these computations are shown in the last three rows of Table 1-2.
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 The Effect of Concentration on the
Titration Curve
The effects of reagent and analyte concentration on the
neutralization titration curves for strong acids are shown by the two
sets of data in Table 14-2 and the plots in Figure 1-3.

Note that with 0.1 M NaOH as the titrant, the change in pH in the
equivalence-point region is large. With 0.001 M NaOH, the change
is much smaller, but still pronounced.
Figure 1-3 Titration curves
for HCl with NaOH.
Curve A: 50.00 mL of
0.0500 M HCl with 0.1000
M NaOH.
Curve B: 50.00 mL of
0.000500 M HCl with
0.001000 M NaOH.
 Choosing an Indicator
Figure 1-3 shows that all three indicators
can be employed when reagent
concentration is around 0.1 M.
When concentrations are more dilute,
0.001 M, only bromothymol blue provides
a satisfactory end point.
Errors in reading the buret are observed
when the range of the indicator does not
overlap well with the endpoint.
 Titrating a Strong Base with a
Strong Acid
Before equivalence point, the solution is basic, and the hydroxide ion
concentration is numerically related to the analytical concentration
of the base.
The solution is neutral at the equivalence point
And beyond equivalence point, it becomes acidic because the
hydronium ion concentration is equal to the analytical concentration
of the excess strong acid.
 Example 1 – 2
Calculate the pH during the titration of 50.00 mL of 0.0500 M NaOH with
0.1000 M HCl at 25°C after the addition of the following volumes of reagent:
(a) 24.50 mL, (b) 25.00 mL, (c) 25.50 mL.
Solution: (a) At 24.50 mL added, [H3O+] is very small and cannot be
computed from stoichiometric considerations but can be obtained
from [OH-]:
VNaOH × CNaOH − VHCl x CHCl
[OH–] = CNaOH =
VNaOH + VHCl
(50.00×0.0500)−(24.50 ×0.1000)
=
50.00+24.50
= 6.71 x 10-4 M
pOH = –log [OH–] = –log (6.7 x 10-4) = 3.17
pH = 14 – pOH = 14 – 3.17 = 10.83
 Example 1 – 2
(b) 25.00 mL added is the equivalence point

[OH–] = [H3O+] = 1 × 10−14 = 1 x 10–7

pH = – log(1.00 x 10-7) = 7.00

 Example 1 – 2
(c) At 25.50 mL added, beyond equivalence point
VH𝐶𝑙 C𝐻𝐶𝑙 − VNaOH × CNaOH
[H3O+] = cHCl =
VNaOH + VHCl

(25.50 x 0.1000) − (50.00 x 0.0500)

= 6.62 x 10-4
50.00+25.50

pH = –log [H3O+]
pH = – log (6.62 x 10-4) = 3.18
 Titrating a
Strong Base with
a Strong Acid
Figure 1-4 Titration curves
for NaOH with HCl.
Curve A: 50.00 mL of 0.0500
M NaOH with 0.1000 M HCl.
Curve B: 50.00 mL of 0.00500
M NaOH with 0.0100 M HCl.

7-45
 Titration Curves For Weak Acids
Four types of calculations are needed to compute values for a weak
acid (or a weak base) titration curve.
1. At the beginning, the solution contains only a weak acid or a weak
base, and the pH is calculated from the concentration of that solute
and its dissociation constant.
2. After various increments of titrant have been added, the solution
consists of a series of buffers. The pH of each buffer can be calculated
from the analytical concentrations of the conjugate base or acid and
the residual concentrations of the weak acid or base. Using the
dissociation constant of the weak acid or base.

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 Titration Curves For Weak Acids
3. At the equivalence point, the solution contains only the conjugate
of the weak acid or base being titrated (that is, a salt), and the pH is
calculated from the concentration of this product.

4. Beyond the equivalence point, the excess titrant, whether it is a

strong base or strong acid, is what affects the pH.

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 Example 1-3
Generate a curve for the titration of 50.00 mL of 0.1000 M acetic acid
(HOAc) with 0.1000 M sodium hydroxide at 25°C. Ka = 1.75 x 10-5
Initial pH

First, we must calculate the pH of a 0.1000 M solution of HOAc

(using the methods we learned on how to get the pH of weak acids in chapter 9: Aqueous
Solutions & Chemical Equilibria)

[H3O+] = √KacHOAc =√1.75 x 10-5 x 0.1000 = 1.32x10-3 M

pH = - log(1.32 x 10-3) = 2.88

pH after Addition of 10.00 mL of Reagent
A buffer solution consisting of NaOAc and HOAc has now been produced.
NaOH + HOAc → NaOAc + H2O
The analytical concentrations of the two constituents are:
(VHOAc ×cHOAc ) −(VNaOH × cNaOH ) 50.00 ×0.1000 −(10.00 ×0.1000)
cHOAc = = =
VHOAc +VNaOH 50.00 + 10.00
4.000
60.00

(VNaOH × cNaOH ) (10.00 ×0.1000) 1.000

CNaOAc = = =
VHOAc +VNaOH 50.00 + 10.00 60.00
Substituting the values into the acid-dissociation expression of acetic
acid:
𝐻3 𝑂+ [𝑂𝐴𝑐 − ]
Ka = = 1.75 x10-5
[𝐻𝑂𝐴𝑐]
4.000
𝐾𝑎 [𝐻𝑂𝐴𝑐] (1.75 ×10−5 ) ( )
[H3O+] = = 1.000
60.00
= 7.00 x 10-5
[𝑂𝐴𝑐 − ]
60.00

pH = –log [H3O+] = –log (7.00 x 10-5) = 4.15

Note that the total volume of solution is present in both numerator and
denominator and thus cancels in the expression for [H3O+].
All calculations before equivalence point may be done this way.
Table 14-3
pH after Addition of 25.00 mL of Reagent

Before equivalence point

(VHOAc ×cHOAc ) −(VNaOH × cNaOH ) 50.00 ×0.1000 −(25.00 ×0.1000) 2.500
cHOAc = = =
VHOAc +VNaOH 50.00 +25.00 75.00

(VNaOH × cNaOH ) (25.00 ×0.1000) 2.500

CNaOAc = = =
VHOAc +VNaOH 50.00 +25.00 75.00

𝐾𝑎 [𝐻𝑂𝐴𝑐] (1.75 ×10−5 ) ×2.500

[H3O+] = = = 1.75 x10-5
[𝑂𝐴𝑐 − ] 2.500

pH = –log [H3O+] = –log (1.75 x10-5) = 4.76

At this half-titration point, the analytical concentrations of the acid and

conjugate base cancel in the expression for [H3O+]
Equivalence-point pH
At the equivalence point, all of the acetic acid has been converted to
sodium acetate. The solution is, therefore, similar to one formed by
dissolving NaOAc in water, and the pH calculation is identical to that
shown for a weak base.
(VNaOH × cNaOH ) (50.00 ×0.1000)
CNaOAc = = = 0.0500 M
VHOAc +VNaOH 50.00 +50.00

OAc- + H2O ⇋ HOAc + OH-

[OH-] = [HOAc]
[Oac-] = 0.0500 - [OH-] = 0.0500
 Substituting these quantities into the base dissociation-constant
expression for OAc- gives
OH− [HOAc] [OH− ]2 Kw
Kb = = =
[OAc− ] [OAc− ] Ka
− −14
− 2
[OAc ] × K w 0.0500 × (1.00 × 10 )
[OH ] = =
Ka (1.75 × 10−5 )

0.0500 ×(1.00 ×10−14 )

[OH-] = = 5.35 x 10-6 M
(1.75 ×10−5 )

pH = 14.00 - [-log(5.35 x 10-6)] = 8.73

Note that the pH at the equivalence point in this titration is greater than 7.
The solution is basic. A solution of the salt of a weak acid is always basic.
pH After Addition of 50.10 mL of Base Note that the titration
Beyond equivalence point the excess base and the curve for a weak acid
acetate ion are both sources of hydroxide ion. with a strong base is
identical with that for
NaOH → OH- + Na+
a strong acid with a
OAc- + H2O ⇋ OH- +HOAc strong base in the
The contribution from the acetate ion is negligible region slightly beyond
the Equivalence
[OH-] = cNaOH + [HOAc] = cNaOH Point.
(VNaOH ×cNaOH ) −(VHOAc × cHOAc )
cNaOH = In a dilute solution,
VNaOH + VHOAc
50.10 ×0.1000 −(50.00 ×0.1000)
some of the
= = 9.99x 10-5 assumptions made in
50.10 + 50.00
this example do not
pH =14.00 - [-log(9.99 x 10-5)] = 10.00
hold.
 Solutions for the titration curve in a titrations of weak acids and bases
are the same for strong acids and bases except for the initial point, the
half-titration point, and the equivalence point.

❖At the half-titration point in a weak-acid titration,

[H3O+] = Ka, and pH = pKa.

❖At the half-titration point in a weak-base titration,

[OH-] = Kb, and pOH = pKb
(recall Kb = Kw /Ka ).
Figure 1-5. Curve for
the titration of acetic acid
with sodium hydroxide.
Curve A: 0.1000 M acid
with 0.1000 M base.
Curve B: 0.001000 M acid
with 0.001000 M base.

7-57
 The Effect of Concentration
The second and third columns of Table 14-3 compare pH data when
using concentrated solutions of weak acid and string base, and using
dilute solutions of weak acid and strong base.

In calculating the values for the more dilute solutions, none of the
approximations shown in Example 1-3 were valid, and solution of a
quadratic equation was necessary for each point on the curve until
after the equivalence point.
 The Effect of Concentration
In the post-equivalence point region, the excess OH- predominates,
and the simple calculation works nicely. Figure 1-5 is a plot of the
data in Table 1-3.

Note that the initial pH values are higher and the equivalence-point
pH is lower for the more dilute solution (Curve B).
 The Effect of Concentration
At intermediate titrant volumes, however, the pH values differ only
slightly because of the buffering action of the acetic acid/sodium acetate
system that is present in this region. Figure 1-5 is graphical confirmation
that the pH of buffers is largely independent of dilution.

Note that the change in [OH-] in the vicinity of the equivalence point
becomes smaller with lower analyte and reagent concentrations. This
effect is analogous to the effect for the titration of a strong acid with a
strong base (see Figure 1-3).
 The Effect of Reaction Completeness
Figure 1-6 The effect of acid
strength (dissociation constant, Ka )
on titration curves.

Each curve represents the titration of

50.00 mL of 0.1000 M acid with
0.1000 M base.

Note that the pH change in the

equivalence-point region becomes
smaller as the acid becomes weaker.

Endpoints are sharper when the Ka is

higher.

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Choosing an Indicator: The Feasibility of Titration
Figures 1-5 and 1-6 show that the choice of indicator is more limited for
the titration of a weak acid than for the titration of a strong acid.
 Titration Curves for Weak Bases
Example 1-4
A 50.00-mL aliquot of 0.0500 M NaCN (Ka for HCN = 6.2 x 10-10) is
titrated with 0.1000 M HCl. Calculate the pH after the addition of (a)
0.00, (b) 10.00, (c) 25.00, and (d) 26.00 mL of acid.
CN- + H3O+ ⇋ HCN + H2O
 Solution: (a) 0.00 mL of Reagent
[OH− ] [HCN] Kw 1.00 ×10−14
Kb = = = = 1.61 x 10-5
[CN− ] Ka 6.2 ×10−14

[OH-] = [HCN]
[CN-] = cNaCN - [OH-] = cNaCN = 0.0500 M
Substituting the [OH-] into the dissociation-constant expression and
rearranging gives,
[OH-] = 𝐾𝑏 𝑐𝑁𝑎𝐶𝑁 = (1.61 × 10−5 ) × .0500 = 8.97 x 10-4 M
pH = 14.00 - [-log(8.97 x 10-4)] = 10.95
 Solution: (b) 10.00 mL of Reagent
Addition of acid produces a buffer with a composition given by
(VNaCN ×cNaCN ) −(VHCl × cHCl ) 50.00 ×0.0500 −(10.00 ×0.1000) 1.500
cNaCN= = =
V𝑁𝑎𝐶𝑁 +V𝐻𝐶𝑙 50.00 +10.00 60.00

(VHCl × cHCl ) (10.00 ×0.1000) 1.000

CHCN = = =
VNaCN +VHCl 50.00 +10.00 60.00

These values are then substituted into the expression for the acid
dissociation constant of HCN to give [H3O+] directly:
𝐾𝑎 [𝐻𝐶𝑁] (6.2 ×10−10 ) ×1.000
[H3O+] = = = 4.3 x10-10 M
[𝑁𝑎𝐶𝑁] 1.500

pH = - log(4.3 X 10-10) = 9.37

 Solution: (c) 25.00 mL of Reagent
This volume corresponds to the equivalence point, where the
principal solute species is the weak acid HCN. Thus,
VHCl + cHCl 25.00 × 0.1000
cHCN = =
VHCl + VNaCN 25.00 + 50.00
cHCN = 0.0333 M

Use the formula for getting [H3O+] of weak acids:

[H3O+] = K a cHCN = (6.2 × 10−10 ) × 0.0333 = 4.55 x10-6 M

pH = -log(4.55 x 10-6) = 5.34

 Solution: (d) 26.00 mL of Reagent
Beyond equivalence point, the excess of strong acid now present
suppresses the dissociation of the HCN to the point where its
contribution to the pH is negligible. Thus,
(VHCl × cHCl ) − (VNaCN × cNaCN )
[H3O+] = cHCl =
VHCl + VNaCN

26.00 ×0.1000 −(50.00 ×0.0500)

= = 1.32 x 10-3 M
26.00+50.00

pH = - log(1.32 x3 10-3) = 2.88

When you titrate a weak base, use an indicator with a mostly acidic
transition range. When titrating a weak acid, use an indicator with a
mostly basic transition range.
Figure 1-7 shows hypothetical titration curves for a series of weak
bases of different strengths. The curves show that indicators with
mostly acidic transition ranges must be used for weak bases.

Figure 1-7. The effect of

base strength (Kb) on
titration curves.
Each curve represents the
titration of 50.00 mL of
0.1000 M base with 0.1000
M HCl.

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The End