ANALYTICAL

CHEMISTRY
FUNDAMENTALS OF ANALYTICAL
CHEMISTRY TENTH EDITION
D. A. Skoog, D. M. West, F. J. Holler, S. R. Crouch,
Cengage Learning Inc.

KIM203E –ITU Chemistry Department

Chapter 13: Titrimetric Methods, Precipitation Titrimetry

Dr. Nejla Çini

Skoog, D. A., West, D. M., & Holler, F. J. (2021). Fundamentals of Analytical Chemistry (10th Edition). Cengage Learning US.
https://bookshelf.vitalsource.com/books/9780357450437
 Titrimetric Methods

• 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 standart solution of a

chemical or an electric current of known
magnitude.
 Titrimetric Methods

• Volumetric titrations involve measuring the volume of

a solution of known concentration that is needed to
react completely with the analyte (the volume of a
standard reagent is the measured quantity).

• 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 (the quantity of charge required
to complete a reaction with the analyte is the
measured quantity).
 SOME TERMS IN VOLUMETRIC TITRIMETRY
• Standard solution (standard
titrant) is a reagent of known
concentration that is used to carry
out a volumetric titration.

• Titration; is a process in
which a standart reagent
is added to a solution of
an analyte until the
reaction between the
analyte and reagent is
judged to be completed.

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 SOME TERMS IN VOLUMETRIC TITRIMETRY
• The titration is
performed by slowly
adding a standard
solution from a
burette to a solution
of the analyte.

• The volume or mass

of reagent needed to
complete the titration
is determined from
the difference
between the initial
and final readings.
Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 SOME TERMS IN VOLUMETRIC TITRIMETRY
• 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.

• The second titration's results show how much of the excess

reagent was used in the first titration and then the original
analyte's concentration can be calculated.

• Back-titrations are often required when the rate of reaction

between the analyte and reagent is slow or when the
standard solution lacks stability, or when direct titration
endpoint would be hard to notice.
SOME TERMS IN VOLUMETRIC TITRIMETRY

e.g. the amount of phosphate in a sample can be determined by adding a

measured excess of standard silver nitrate to a solution of the sample,
which leads to the formation of insoluble silver phosphate
PO43- + 3 Ag+ → Ag3PO4(s)

Then, the excess of standard AgNO3 is back-titrated with standard KSCN:

Ag + + SCN- → AgSCN(s)

The amount of silver nitrate is chemically equivalent to the amount of

phosphate ion plus the amount of thiocyanate used for the back-
titration. The amount of phosphate is then the difference between the
amount of silver nitrate and the amount of thiocyanate.
 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 in a titration is a theoretical point reached

when the amount of added titrant is chemically equivalent to the
amount of analyte in the sample

The equivalence point of a titration is estimated by observing

some physical change associated with the condition of chemical
equivalence called the end point for the titration.

The end point is the point in a titration when a physical change

occurs that is associated with the condition of chemical
equivalence.
 Titration error, Et,

• In volumetric methods, the titration error, Et, is given by

Et = Vep - Veq

Vep : actual volume of reagent required to reach the end point

Veq : the theoretical volume necessary to reach the equivalence point

The difference in volume or mass between the

equivalence point and the end point is the titration error.
 Indicators
Indicators are often added to the analyte solution to
produce an observable physical change (signaling the end
point) at or near the equivalence point.

Large changes in the relative concentration of analyte or

titrant occur in the equivalence-point region.

These concentration changes cause the indicator to

change its appearance.

Typical indicator changes include the appearence or

disappearence of a color, a change in color, or the
appearance or disappearance of turbidity.
Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
Petrucci, R. H.; Herring F. G.; Madura, F. D.; Bissonnette, C., 2010, General Chemistry, Principles and Modern Applications, 10th Edition, Pearson Prentice Hall. Upper
Saddle River, N. J.
Petrucci, R. H.; Harwood, W. S.; Herring F. G., 2002, General Chemistry, Principles and Modern Applications, 8th Edition, Pearson Prentice Hall. Upper Saddle River, N. J.
 Standard Solutions
A standard solution in which the concentration is known with great precision
and which reacts stoichiometrically with the analyte.

The ideal standard solution for a titrimetric method will:

1. be sufficiently stable so that it is necessary to determine its concentration
only once;
2. react rapidly with the analyte so that the time required between additions
of reagent is minimized;
3. react more or less 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

Standard solutions are referred to either as primary standards or secondary

standards.
 Standard Solutions: Primary Standard
A primary standard is a highly purified compound that serves as a
reference material in titrations and in other analytical methods.
The accuracy of a method critically depends on the properties of
the primary standard.
Primary standards can be prepared by weighing directly and
dissolving to a measured volume the reagent which is to react
with the analyte.
Important requirements for a primary standard are the following:
 high purity, low reactivity, atmospheric stability non-toxic
 Reasonable solubility in the titration medium.
 Reasonably large molar mass (high equivalent weight)so that the relative
error associated with weighing the standard is minimize
 Absence of hydrate water so that the composition of the solid does not
change with variations in humidity
 Absence of hydrate water so that the composition of the solid does not
change with variations in humidity
 inexpensive and readily available
 Standard Solutions: Secondary Standard

Secondary standard is a chemical whose purity has

been established by chemical analysis

• Very few compounds meet or even approach these

criteria, and only a limited number of primary-
standard substances are available commercially.
• Less pure compounds must sometimes be used in
place of a primary standart.
• The purity of such a secondary standard must be
established by careful analysis.
• Serves as the reference material for the titrimetric
methods.
 Standard Solutions
Two basic methods are used to establish the concentration of such
solutions.
1. Direct method in which a carefully determined mass of a primary
standard is dissolved in a suitable solvent and diluted to a known
volume in a volumetric flask.
2. Standardization method: in which the titrant to be standardized is
used to titrate (1) a known mass of a primary standard, (2) a known
mass of a secondary standard, or (3) a measured volume of another
standard solution

In a standardization, the concentration of a volumetric solution is

determined by titrating it against a carefully measured quantity of a
primary or secondary standard or an exactly known volume of
another standard solution.
A titrant that is standardized is sometimes referred to as a secondary
standard solution.
 Standardization Titration

titrant
titrant (known
(unknown concentration)
concentration)

analyte
(unknown
Primer standard concentration)
(known
concentration)

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Volumetric Calculations
We can express the concentration of solutions in several ways.

For the standard solutions used in most titrations, either molar

concentration, C, or normal concentration, CN, is usually used.

Molar concentration, C is the number of moles of reagent

contained in one liter of solution,
Most volumetric calculations are based on two pairs of simple
equations that are derived from definitions of the mole, the millimole,
and the molar concentration. For the chemical species A, we can write

where nA is the amount of A, mA is the mass of A, and MA is the molar mass of A.

 Volumetric Calculations

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Volumetric Calculations

normal concentration, CN is the number of equivalents

of reagent in the same volume.
EXAMPLE 13-1

• Describe the preparation of 2.000 L of 0.0500 M

AgNO3 (169.87 g/mol) from the primary standard
grade solid.
EXAMPLE 13-1

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-2

• A standard 0.0100 M solution of Na+ is required to

calibrate an ion-selective electrode method to
determine sodium. Describe how 500 mL of this
solution can be prepared from primary standard
Na2CO3 (105.99 g/mol)
EXAMPLE 13-2

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-3

How would you prepare 50.0 mL portions of standard

solutions that are 0.00500 M, 0.00200 M, and
0.00100 M in Na+ from 0.0100 M solution of Na+ ?
EXAMPLE 13-3

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-3

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-4

A 50.00 mL portion of an HCl solution required 29.71

mL of 0.01963 M Ba(OH)2 to reach an end point with
bromocresol green indicator.
Calculate the molarity of the HCl.
EXAMPLE 13-4

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-4

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-5

• Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol)

required 43.31 mL of KMnO4. What is the molarity of
the KMnO4 solution? The chemical reaction is

2 MnO4-(aq) + 5 C2O4-2(aq) + 16 H+(aq)  2 Mn+2(aq) + 10 CO2(g) + 8 H2O

EXAMPLE 13-5

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-6

A 0.8040 g sample of an iron is dissolved in acid. The iron is

then reduced to Fe2+ and titrated with 47.22 mL of 0.02242
M KMnO4 solution.

Calculate the result of this analysis in terms of

(a) %Fe (55.847 g/mol)

(b) %Fe3O4 (231.54 g/mol)
EXAMPLE 13-6

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-6

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-7

A 100 mL sample of brackish water was made

ammoniacal, and the sulfide it contained was titrated
with 16.47 mL of 0.02310 M AgNO3.
Calculate the concentration of H2S (34.081 g/mol) in
the water in parts per million (ppm) at the end point.

2Ag+ + S2- Ag2S

EXAMPLE 13-7

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-8

The phosphorus in a 4.258 g sample of a plant food was

converted to PO43_ and precipitated as Ag3PO4 through
the addition of 50.00 mL of 0.0820 M AgNO3. The excess
AgNO3 was back titrated with 4.06 mL of 0.0625 M KSCN.
Express the result of this analysis in terms of %P2O5.
P2O5: 141. 9 g/mol
EXAMPLE 13-8
The chemical reactions are:
P2O5 + 9H2O → 2PO43- + 6H3O+

2PO43- + 6Ag+ → 2Ag3PO4(s)

(excess)
Ag+ + SCN- → AgSCN(s)

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-8

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-9

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-9

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 13-9

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Gravimetric titrations

Mass (weight) or gravimetric titrations differ from their volumetric

counterparts in that the mass of titrant is measured rather than the
volume.
The most common way to express concentration for mass titrations
is the weight concentration, Cw, in weight molar concentration units,
Mw, which is the number of moles of a reagent in one kilogram of
solution or the number of millimoles in one gram of solution.

The weight molarity CW(A) of a solution of a solute A is:

 Advantages of Gravimetric titrations

Calibration of glassware and cleaning are eliminated

 Temperature corrections are unnecessary because the
mass (weight) molar concentration does not change with
temperature, in contrast to the volume molar concentration.
This advantage is particularly important in non-aqueous
titrations because of the high coefficients of expansion of
most organic liquids (about 10 times that of water)
Weight measurements can be made with greater
precision and accuracy than volume measurements.
 Gravimetric titrations are more easily automated than
volumetric titrations.
 Titration curves in Titrimetric Methods

Titration curves are plots of a concentration- related

variable as a function of reagent volume.
The most widely used end points involve:
1) changes in color due to the reagent, analyte, or an
indicator
2) a change in potential of an electrode that responds
to the concentration of the reagent or the analyte
A titration curve is a plot of some function of the analyte or
titrant concentration on the y axis versus titrant volume on the x
axis.
 Types of Titration Curves

Two general types of titration curves (two general

types of end points) are encountered in titrimetric
methods:

I. A sigmoidal curve
II. A linear segment curve

To construct titration curves, three type of calculations is

required: pre-equivalence, equivalence and post-equivalence
 Types of Titration Curves
Sigmoidal curve
The vertical axis in a
sigmoidal titration curve is
either the p-function of the
analyte or titrant or the
potential of an analyte- or
titrant-sensitive electrode.
The p-function of analyte
(sometimes reagent) is
plotted as a function of
reagent volüme.
Important observations are
confined to a small region
surrounding the equivalence
point.
It offers the advantages of
speed and convenience.

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Types of Titration Curves
Linear-segment curve
The vertical axis of a linear
segment titration curve is an
instrument signal that is
proportional to the concentration
of the analyte or titrant.
Measurements are made on both
sides of, but well away from the
eqivalance point.
Measurements near equivalence
are avoided.
It offers the advantages for of
speed and convenience.
It is advantages for reactions that
are complete only in the presence
of a considerable excess of the
reagent or analyte.

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Concentration Changes during Titrations

The equivalence point in a

titration is characterized by
major changes in the relative
concentrations of the
reagent and analyte.

The large changes in relative

concentration that occur in
the region of chemical
equivalence are shown by
plotting the negative
logarithm of the analyte or
the ragent concentration Titration curve of pH and pOH for the
(the p-function) against titration of 0.1000M HCl with 0.1000 M
reagent volume NaOH

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Precipitation titration
(Chapter 13F in 8th Ed. or Chapter 17B-2 in 9th Ed.)

• Precipitation titrations are based on reactions that yield

ionic compounds of limited solubility.
• The slow rate at which most precipitates form,
however, limits the number of precipitating agents that
can be used in titrations to a handful.
• We limit our discussion here to the most widely used
and important precipitating reagent, silver nitrate,
which is used for the determination of the halogens,
the halogenlike anions, mercaptans, fatty acids, and
several divalent inorganic anions.
• Titrations with silver nitrate are sometimes called
argentometric titrations.
 Precipitation Titration Curves Involving Silver Ion

• The most common method of determining the halide

ion concentration of aqueos solutions is titration with a
standard solution of AgNO3 is Argentometry.
• In this methos, the reaction product is solid silver
halide
• Most indicators for argentometric titrations respond to
changes in the concentrations of silver ions. Because of
this response, titration curves for precipitation
reactions usually consist of a plot of pAg versus the
volume of AgNO3.
To construct titration curves, three type of calculations is
required: pre-equivalence, equivalence and post-equivalence
EXAMPLE 17-1

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 17-1

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 17-1
EXAMPLE 17-1

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
EXAMPLE 17-1

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 The Effect of Concentration on Titration Curves
With 0.1000 M AgNO3 (Curve A), the
change in pAg in the equivalence-point
region is large, about 2 pAg units.

With the 0.01000 M reagent, the change is

about 1 pAg unit, but still pronounced.

For the more dilute chloride solution

(Curve B), the change in pAg in the
equivalence-point region would be drawn
out over a fairly large volume of reagent
(,3 mL as shown by the dashed lines in the
figure) so that to determine the end point
accurately would be impossible.

reagent conc. ↑ → sharpness ↑

Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
Effect of reaction completeness on titration curves
This figure illustrates the effect of
solubility product on the sharpness of
the end point for titrations with 0.1 M
silver nitrate. Note that the change in
pAg at the equivalence point becomes
greater as the solubility products become
smaller, that is, as the reaction between
the analyte and silver nitrate becomes
more complete.

Note that ions forming precipitates with

solubility products much larger than
about 10-10 do not yield satisfactory end
points.

reaction completeness :
product precipitate Ksp ↓ → sharpness ↑
Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
Effect of reaction completeness on titration curves

reaction completeness :
product precipitate Ksp ↓ → sharpness ↑
Skoog, D. A., West, D. M., Holler, F. J., Crouch, S. R. (2022). Fundamentals of Analytical Chemistry (10h Edition). Brooks/Cole Cengage Learning US.
 Indicators for Argentometric Titrations

The end point produced by chemical indicator

consist of a color change or the appearance or
disappearance of turbidity in the solution being
titrated

The requirements for an indicator for a

precipitation titration are that :
1) The color change should occur over a limited
range in p-function of the reagent or the
analyte
2) The color change should take place within the
steep portion of the titration curve for the
analyte
 Indicators for Argentometric Titrations
There are three common types of precipitation titrations in
argentometry
1. Mohr Method - CrO42- indicator
(yellow to red)

2. Fajans Method - adsorption indicator = dichlorofluorescein anion

(pink at endpoint)

3. Volhard Method - back titration of excess Ag+ with SCN-, Fe3+

indicator
(clear to red)
 Indicators for Argentometric Titrations
1. The Mohr method-Chromate Ion;
In the Mohr method, sodium chromate serves as the indicator for
the argentometric titration of chloride, bromide, and cyanide ions.

Silver ions react with chromate to form the brick-red silver

chromate (Ag2CrO4) precipitate in the equivalence-point region
sample: Cl-, Br-, CN-

Titration reaction Ag+ + Cl_ ⇋ AgCl

White ppt.

Indicator reaction 2Ag+ + CrO42_ ⇋ Ag2CrO4

yellow Brick red ppt.
 Indicators for Argentometric Titrations
2. Fajans Method-Adsorption indicators
Adsorption indicators were first described by K. Fajans, a Polish chemist in 1926.

Titrations involving adsorption indicators are rapid, accurate, and reliable, but their
application is limited to the few precipitation titrations that form colloidal
precipitates rapidly.

The Fajans method uses an adsorption indicator, an organic compound that adsorbs
onto or desorbs from the surface of the solid in a precipitation titration. Ideally, the
adsorption or desorption occurs near the equivalence point and results not only in a
color change but also in the transfer of color from the solution to the solid or vice versa.

Fluorescein is a typical an adsorption indicator that tends to be adsorbed onto the

surface of the solid in a precipitation titration. It is used in the titration of Cl- ion with
silver nitrate.
 Indicators for Argentometric Titrations
3. Volhard method-Iron(III) Ion
• The Volhard method is one of the most common argentometric
methods. In this method, silver ions are titrated with a standard
solution of thiocyanate ion:
Ag+ + SCN- ⇋ AgSCN(s)

Iron(III) serves as the indicator. The solution turns red with the first
slight excess of thiocyanate ion due to the formation of Fe(SCN)2+

Fe3+ + SCN- ⇋ FeSCN2+

Titration must be carried out in acidic solution to

prevent precipitation of iron (III) as the hydrated oxide.
 Indicators for Argentometric Titrations
3. Volhard method-Iron(III) Ion
1. A measured excess of standard silver nitrate solution is
added to the sample, and the excess Ag+ is determined by
back-titration with a standard thiocyanate (KSCN) solution
using Fe3+ as the indicator.
2. The strongly acidic environment of the Volhard titration is a
distinct advantage over other titrations of halide ions because
such ions as carbonate, oxalate, and arsenate do not
interfere.
3. The silver salts of these ions are soluble in acidic media but
only slightly soluble in neutral media. Silver chloride is more
soluble than silver thiocyanate.

Ag+ + SCN- ⇋ AgSCN(s)

Fe3+ + SCN- ⇋ FeSCN2+