Chapter 2

Chemical equilibrium and

classical methods for analysis
- Gravimetric methods and Titrations

Holler, Crouch, Skoog and Wests Fundamentals of Analytical Chemistry, 9th Ed., Brook/Cole, 2014.
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Among the strong electrolytes listed are acids, bases, and salts.
A salt is produced in the reaction of an acid with a base.
Ex., NaCl, Na2SO4, and NaOOCCH3 (sodium acetate).
Acids and bases
According to the Brnsted-Lowry theory, an acid is a proton donor, and a
base is a proton acceptor. For a molecule to behave as an acid, it must
encounter a proton acceptor (or base) and vice versa.
Conjugate Acids and Bases
A conjugate base is formed when an acid loses a proton.
For example, acetate ion is the conjugate base of acetic acid.
A conjugate acid is formed when a base accepts a proton.
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Acids and bases

Acid1 and base1 act as a conjugate acid/base pair, or just a conjugate pair.
Similarly, every base accepts a proton to produce a conjugate acid. When
these two processes are combined, the result is an acid/base, or
neutralization reaction.
This reaction proceeds to an extent that depends on the relative
tendencies of the two bases to accept a proton (or the two acids to
donate a proton).

Water/ Aqueous solution

An aqueous solution of ammonia

Ammonia (base1) reacts with water (acid2) to give the conjugate acid
ammonium ion (acid1) and hydroxide ion (base2) of the acid water.

An aqueous solution of nitrous acid

Water acts as a proton acceptor, or base

The conjugate base of the acid HNO2 is nitrite ion.
The conjugate acid of water is the hydrated proton written as H3O+.
This species is called the hydronium ion, and it consists of a proton
covalently bonded to a single water molecule.

Water is the classic example of an amphiprotic solvent.

(Species that have both acidic and basic properties are amphiprotic. )
Common amphiprotic solvents include methanol, ethanol, and
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anhydrous acetic acid.

Chemical equilibrium
Many reactions never result in complete conversion of reactants to
products. They proceed to a state of chemical equilibrium in which
the ratio of concentrations of reactants and products is constant.
Equilibrium-constant expressions are algebraic equations that
describe the concentration relationships among reactants and
products at equilibrium.
The Equilibrium State
The final position of a chemical equilibrium is independent of the
route to the equilibrium state.
This relationship can be altered by applying stressors such as
changes in temperature, in pressure, or in total concentration of a
reactant or a product.
These effects can be predicted qualitatively by the Le Chteliers
principle.
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Types of Equilibrium Constants in Analytical Chemistry

Buffer solutions
A buffer solution resists changes in pH when it is diluted or when
acids or bases are added to it.
Bsolutions are prepared from a conjugate acid/base pair.
Buffers are used in chemical applications whenever it is important
to maintain the pH of a solution at a constant and predetermined
level.

The effect of dilution

Calculating the pH of Buffer Solutions

A solution containing a weak acid, HA, and its conjugate base, A-, may be acidic,
neutral, or basic, depending on the positions of two competitive equilibria:

These two equilibrium-constant expressions show that the relative

concentrations of the hydronium and hydroxide ions depend not only on
the magnitudes of Ka and Kb but also on the ratio between the
concentrations of the acid and its conjugate base.
To find the pH of a solution containing both an acid, HA, and conjugated
base (NaA), the equilibrium concentrations of HA and NaA need to
expressed in terms of their analytical concentrations, CHA and CNaA.

The dissociation-constant expression can then be expressed as:

The hydronium ion concentration of a solution containing a weak acid

and its conjugate base depends only on the ratio of the molar
concentrations of these two solutes.
Furthermore, this ratio is independent of dilution because the
concentration of each component changes proportionally when the
volume changes.

The Henderson-Hasselbalch Equation

- calculate the pH of buffer solution

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The effect of Added Acids and Bases

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Buffers do not maintain pH at an absolutely constant value, but changes

in pH are relatively small when small amounts of acid or base are added.

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Gravimetric Methods of Analysis

Gravimetric methods are quantitative methods that are based on

determining the mass of a pure compound to which the analyte is
chemically related.
They are based on mass measurements with an analytical balance, an
instrument that yields highly accurate and precise data.
In precipitation gravimetry, the analyte is separated from a solution
of the sample as a precipitate and is converted to a compound of
known composition that can be weighed.
In volatilization gravimetry, the analyte is separated from other
constituents of a sample by converting it to a gas of known chemical
composition. The mass of the gas then serves as a measure of the
analyte concentration.
In electrogravimetry, the analyte is separated by deposition on an
electrode by an electrical current. The mass of this product then
provides a measure of the analyte concentration
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Calculation of results from gravimetric data

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Applications of gravimetric methods

Gravimetric methods do not require a calibration or standardization

step because the results are calculated directly from the
experimental data and atomic masses.
Thus, when only one or two samples are to be analyzed, a
gravimetric procedure may be the method of choice because it
requires less time and effort than a procedure that requires
preparation of standards and calibration.

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Inorganic Precipitating Agents

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Reducing Agents

Reducing agents: convert an analyte to its elemental form for weighing.

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Organic Precipitating Agents

There are two types of organic reagents: one forms slightly soluble
nonionic products called coordination compounds, and the other
forms products in which the bonding between the inorganic
species and the reagent is largely ionic.
Organic reagents that yield sparingly soluble coordination compounds
typically contain at least two functional groups.
Each of these groups is capable of bonding with a cation by donating a
pair of electrons.
The functional groups are located in the molecule such that a five- or
six-membered ring results from the reaction.
Reagents that form compounds of this type are called chelating agents,
and their products are called chelates.
Metal chelates are relatively nonpolar and have solubilities that are low
in water but high in organic liquid.
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Chelates
Chelates are cyclical metal-organic compounds in which the metal is a
part of one or more five- or six-membered rings.
Heme is a part of homoglobin, the oxygen-carrying molecule in human
blood. The four six-membered rings ate formed with Fe2+.

Heme

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Widely used chelating agents

8-hydroxyquinoline (oxine)

Dimethylglyoxine

Considerable degree of selectivity in the use of

8-hydroxyquinoline by controlling pH.

Sodium Tetraphenylborate

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Organic Functional Group Analysis

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Titrations in Analytical Chemistry

Titration methods are based on determining the quantity of a reagent

of known concentration that is required to react completely with the
analyte.
The reagent may be a standard solution of a chemical or an electric
current of known magnitude.
Volumetric titrations involve measuring the volume of a solution of
known concentration that is needed to react completely with the
analyte.
In Gravimetric titrations, the mass of the reagent is measured instead
of its volume.
In coulometric titrations, the reagent is a constant direct electrical
current of known magnitude that consumes the analyte.

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Equivalence Points and End Points

The equivalence point is the point in a titration when the amount of

added standard reagent is equivalent to the amount of analyte.
The equivalence point of a titration cannot be determined
experimentally.
It can only be estimated by observing some physical change
associated with the condition of chemical equivalence called the end
point for the titration.
The difference in volume or mass between the equivalence point and
the end point is the titration error.
Indicators are often added to the analyte solution to produce an
observable physical change (signaling the end point) at or near the
equivalence point.
The titration error is given as: Et = Vep Veq
where Vep is the actual volume of reagent required to reach the end point
and Veq is the theoretical volume necessary to reach the equivalence point.
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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.

Solutions and indicators for acid/base titrations

Neutralization titrations depend on a chemical reaction of the analyte with a

standard reagent. There are several different types of acid/base titrations.

1. The titration of a strong acid, such as hydrochloric or sulfuric acid, with a

strong base, such as sodium hydroxide.
2. The titration of a weak acid, such as acetic or lactic acid, with a strong base.
3. The titration of a weak base, such as sodium cyanide or sodium salicylate,
with a strong acid.

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Standard Solutions

The standard reagents used in acid/base titrations are always strong

acids or strong bases, such as HCl, HClO4, H2SO4, NaOH, and KOH.
Weak acids and bases are never used as standard reagents because
they react incompletely with analytes.
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.

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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 base or
its conjugate acid form.
For example, the behavior of an acid-type indicator, HIn:
HIn + H2O In- + H3O+

The equilibrium for a base-type indicator, In:

In + H2O InH+ + OH-

The equilibrium-constant expression for the dissociation of an acidtype indicator takes the form
Ka = [H3O+][In-]
[HIN]

[H3O+] =Ka [HIN]

[In-]
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Figure 14-1 Color change and molecular modes for phenolphthalein.

(a) Acidic form after hydrolysis of the lactone form. (b) Basic form.
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 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.
HIn, exhibits its pure acid color when [HIn]/[In-] 10/1 and its base
color when [HIn]/[In-] 1/10
The range of hydronium ion concentrations needed for the indicator
to change color can be estimated. For full acid color, [H3O+] = 10Ka;
and for the full base color, [H3O+] = 0.1Ka
To obtain the indicator pH range, we take the negative
logarithms of the two expressions:
pH (acid color) = -log(10Ka) = pKa - 1
pH (basic color) = -log(0.1Ka) = pKa + 1
Indicator pH range = pKa 1
An indicator with an acid dissociation constant of 1x10-5
(pKa=5) typically shows a complete color change the pH
of the solution in which it is dissolved changes from 4 to 6.
Indicator color as a function of pH (pKa=5.0).
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Titration Errors with Acid/Base Indicators

There are two types of titration error in acid/base titrations:
Determinate error that occurs when the pH at which the indicator
changes color differs from the pH at the equivalence point. It can
usually be minimized by choosing the indicator carefully or by
making a blank correction.
Indeterminate error that originates from the limited ability of the
human eye to distinguish reproducibly the intermediate color of the
indicator. The magnitude of this error depends on the change in pH
per milliliter of reagent at the equivalence point, on the
concentration of the indicator, and on the sensitivity of the eye to
the two indicator colors.
Variables That Influence the Behavior of Indicators
The pH interval over which a given indicator exhibits a color change is
influenced by temperature, the ionic strength of the medium, and the presence
of organic solvents and colloidal particles. Some of these effects can cause the
transition range to shift by one or more pH units.
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The Common Acid/Base Indicators

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Titration of strong acids and bases

The hydronium ions in an aqueous solution of a strong acid have two
sources:
(1) the reaction of the acid with water
(2) the dissociation of water itself.
For a solution of HCl with a concentration greater than about 10-6 M:
[H3O+] = cHCL + [OH-] cHCL
where [OH-] represents the contribution of hydronium ions from the
dissociation of water.
For a solution of a strong base, such as sodium hydroxide:
[OH-] = cNAOH + [H3O+] cNAOH

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Titrating a Strong Acid with a Strong Base

Three types of calculations must be done to construct the hypothetical
curve for titrating a solution of a strong acid with a strong base.
Preequivalence: compute the concentration of the acid from its
starting concentration and the amount of base added.
Equivalence: the hydronium ion concentration can be calculated
directly from the ion-product constant for water, Kw.
Postequivalence: the analytical concentration of the excess base is
computed, and the hydroxide ion concentration is assumed to be
equal to or a multiple of the analytical concentration.
Kw = [H3O+][OH-]
-log Kw = -log [H3O+][OH-] = -log[H3O+] log[OH-]
pKw = pH + pOH
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The Effect of Concentration/Choosing an Indicator

The effects of reagent and analyte concentration on the neutralization

titration curves for strong acids are shown in Table 14-2 and Figure 14-3.

Figure 14-3 shows that the selection of an

indicator is not critical when the reagent
concentration is approximately 0.1 M.
The volume differences in titrations with
the three indicators shown are of the same
magnitude as the uncertainties associated
with reading the buret and so are
negligible.
The bromocresol green (also phenolphalein)
is unsuited for a titration involving the
0.001M reagent because the color change
occurs over a 5-mL range well before the
equivalence point.
Bromocresol blue provides a satifactory
end point with a minimal systematic error
in the titration of 0.001M NaOH.

Figure 14-3 Titration curves for HCl with NaOH.

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Titrating a Strong Base with a Strong Acid

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Figure 14- 4 Titration curves for NaOH with HCl. Curve A: 50.00 mL of 0.0500M NaOH
with 0.1000M HCl. Curve B: 50.00 mL of 0.00500M NaOH with 0.01000M HCl.
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Titration curves for weak acids

Four distinctly different 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 (up to, but not
including, the equivalence point), 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 concentrations of the weak acid or
base that remains.
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 of strong acid or base titrant
suppresses the acidic or basic character of the reaction product to such an
extent that the pH is governed largely by the concentration of the excess
titrant.
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Hydronium Ion Concentration of Solutions of Weak Acids

When the weak acid HA is dissolved in water, two equilibria produce hydronium ions:

The hydronium ions produced from the first reaction suppress the dissociation of
water to such an extent that the contribution of hydronium ions from the second
equilibrium is negligible.

The sum of the molar concentrations of the weak acid and its conjugate base must
equal the analytical concentration of the acid cHA
Thus, we get the mass-balance equation
Substituting [H3O+] for [A-] yields
which rearranges to

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Thus, the equilibrium-constant expression becomes

Which rearranges to

The positive solution to this quadratic equation is

Assume: dissociation does not appreciably decrease the molar conc. of HA

This can be simplified and expressed as

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The analytical concentrations of acid and

conjugate base are identical when an acid has
been half neutralized.
At the half-titration point in a weak-acid
titration,
[H3O+] = Ka and pH = pKa
In the titration of a weak base, the hydroxide
ion concentration is numerically equal to the
dissociation constant of the base at the
midpoint in the titration curve.
In addition, the buffer capacities of each of the
solutions are at a maximum at this point. These
points, often called the half-titration points.
At the half-titration point in a weak-base
titration,
[OH-] = Kb, and pOH = pKb (recall Kb=Kw/Ka)

Figure 14-5 Curve for the titration of acetic

acid with sodium hydroxide. Curve A: 0.1000M
acid with 0.1000M base. Curve B: 0.00100M
acid with 0.01000M base.

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The Effect of Concentration

The initial pH values are higher and the equivalence-point pH is lower for
the more dilute solution (Curve B).
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.

The Effect of Reaction Completeness

Titration curves for 0.1000 M
solutions of acids with different
dissociation constants are shown.
The pH change in the equivalencepoint region becomes smaller as the
acid becomes weaker.

Choosing an Indicator
The choice of indicator is more
limited in the cases of Figures 14-5
and 14-6.
Figure 14-6 The effect of acid strength (dissociation constant) on titration curves. Each curve
represents the titration of 50.00 mL of 0.1000M weak acid with 0.1000M strong base.
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Titration curves for weak bases

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The effect of base strength (Kb) on titration curves

Each curve represents the titration of 50.00

mL of 0.1000M base with 0.1000M HCl.

Figure 14-7 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.
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The composition of solutions during acid/base titrations

The changes in composition that occur while a solution of a weak acid or a
weak base is being titrated can be visualized by plotting the relative
equilibrium concentration 0 of the weak acid as well as the relative
equilibrium concentration of the conjugate base 1 as functions of the pH of
the solution.

Figure 14-8 Plots of relative amounts of acetic acid and acetate ion during a titration.
The straight lines show the change in relative amounts of HOAc (0) and OAc- (1)
during the titration of 50.00 mL of 0.1000 M acetic acid. The curved line is the
titration curve for the system.

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The Composition of Buffer Solutions as a Function of pH: Alpha Values

The composition of buffer solutions can be visualized by plotting the
relative equilibrium concentrations of the two components of a conjugate
acid/base as a function of the pH of the solution. These relative concentrations
are called alpha values.
If cT is the sum of the analytical concentrations of acetic acid and sodium acetate
in a typical buffer solution, we can write:
0 the fraction of the total concentration of acid that is undissociated
1, the fraction dissociated

Alpha values are unitless ratios whose sum must equal unity. These values depend
only on [H3O+] and Ka.

The re-arranged equation becomes

[HOAc]/cT = 0 Thus,

Similarly,

Figure 9-5 Variation in with pH. Note that

most of the transition between 0 and 1
occurs within 1 pH unit of the crossover
point of the two curves. The crossover point
where 0 = 1 = 0.5 occurs when pH =
pKHOAc = 4.74.

Locating Titration End point from pH Measurements

Figure 14F-4 (a) the titration curve of 50.00 mL of 0.1000 M weak acid with 0.1000 M NaOH
is shown as collected by a pH meter. (b) The second derivative is shown on expanded scale.
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