Volumetric Analysis: Dr. Kathlia A. de Castro-Cruz Analytical Chemistry 1

Volumetric Analysis
Dr. Kathlia A. De Castro-Cruz

Analytical Chemistry 1
Volumetric Analysis
Ø This method involves the measurement of the
volume that will react with the analyte
completely.
Ø A standard solution (titrant) is used to titrate
the sample (analyte).
ü A standard solution is a solution of known
concentration.
ü It must be stable, reacts rapidly and completely
with the analyte and its reaction with the
analyte can be described by a simple chemical
equation.
kadecastro-cruz 2 Volumetric Analysis
Volumetric Analysis
Ø Standardization
ü A method of determining the exact
concentration of a standard solution
ü Maybe done using:
v Direct Method - the concentration of a
standard solution is done by
standardization using a primary standard.
v Indirect Method - The concentration of a
standard solution is done by
standardization using a secondary standard.

Volumetric Analysis
Ø Primary Standard
ü It is an ultrapure compound that serves as the
reference material for a titration or for another
type of quantitative analysis.
ü Characteristics:
v High purity. Established methods for
confirming purity should be available.
v Atmospheric stability.
v Absence of hydrate water so that the
composition of the solid does not change
kadecastro-cruz
with variations in4 humidity. Volumetric Analysis
Volumetric Analysis
Ø Primary Standard
ü Characteristics:
v Readily available at modest cost
v Reasonable solubility in the titration
medium.
v Reasonably large molar mass so that the
relative error associated with weighing the
standard is minimized.

Volumetric Analysis
Ø Common Acidic Primary Standards:
Name Structure FW
Potassium hydrogen phthalate COOH

204.221
(KHP)
COOK
Hydrochloric acid HCl 36.461
Potassium hydrogen iodate KH(IO3)2 389.912
Benzoic acid COOH

122.121
OH OH
COOH CO2K
Sulfosalicyclic acid double salt 550.639
SO3K SO3K
Sulfamic acid H3N+SO3- 97.094

Oxalic acid
HOOC-COOH 90
H2C2O4 + 2HO– ® C2O4–2 + 2H2O
Volumetric Analysis
Ø Common Basic Primary Standards:
Name Structure FW
Tris(hydroxymethyl)amino methane
H2NC(CH2OH) 3 121.135
(tris or THAM)
Mercuric oxide
HgO + 4I– + H2O ® HgI4–2 + 2HO– HgO 216.59
HO–+ H3O+ ® 2H2O
Sodium carbonate
Na2CO3 105.988
CO3–2+2H3O+® 3H2O+CO2
Sodium tetraborate decahydrate

(Borax) Na2B4O7 10H2O 381.372
B4O7–2 + 2H3O+ + 3H2O ® 4 H3BO3

Volumetric Analysis
Ø Secondary Standard
ü It is a compound whose purity has been
determined by chemical analysis.
ü It serves as the working standard material for
titrations and for many other analyses.
ü The concentration of a secondary-standard
solution is subject to a larger uncertainty than is
the concentration of a primary-standard solution.

Volumetric Analysis
Ø Titration Method
ü Direct Titration – a process where an analyte
concentration is determine using exact amount of
standard solution
ü Indirect Titration or Back Titration
v It 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.
v It is often required when the rate of reaction
between the analyte and reagent is slow or when
the standard solution lacks stability.

Volumetric Analysis
Ø Equivalence Points and End points
ü 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.
ü End point is the point in a titration when a
physical change occurs that is associated with the
condition of chemical equivalence.
ü Titration Error - the difference in volume or mass
between the equivalence point and the end point:
Et =Vep - Veq
Volumetric Analysis
Ø Indicators
ü Often added to the analyte solution to produce an
observable physical change (signaling the end
point) at or near the equivalence point.
ü Indicator changes include the appearance or
disappearance of a color, a change in color, or the
appearance or disappearance of turbidity.
ü Can use instruments that respond to properties of
the solution such as colorimeters, turbidimeters,
spectrophotometers, temperature monitors,
refractometers, voltmeters, current meters, and
conductivity meters.
Titrimetry: Volumetric Analysis
Ø Desirable properties of ideal standard solutions
for titrimetric method
ü Be sufficiently stable so that it is only necessary to
determine its concentration once
ü React rapidly with the analyte so that the time
required between additions of reagent is
minimized
ü React completely with the analyte so that
satisfactory end points are realized
ü Undergo a selective reaction with the analyte that
can be described by a balanced equation
Ø Classification according to the type of reaction
involved
ü Acid-base titration – acidic or basic titrant reacts
with the acidic or basic analyte
ü Complexometric titration – involves metal-ligand
complexation
ü Redox titration - titrants can be an oxidizing or
reducing agent wherein the reaction involves
electron transfer
ü Gravimetric titration– analyte and titrant react to
form precipitate which is then measured.
Ø Classification according to the type of reaction
involved
ü Coulometric titration- the quantity of charge
required to complete a reaction with the analyte is
the measured quantity.
ü Amperometric titration – equivalence point is
determined through measurement of the electrical
current produced by the titration reaction
ü Spectrophotometric titration – absorbance is
measured against the volume of titrant used

Preparation of solutions
Ø Sample Problem 1: Describe the preparation of 2.000 L
of 0.0500 M AgNO3 (169.87 g/mol) from the primary-
standard-grade solid.
Ø Sample Problem 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/mL).
Ø 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 0.0100M Na+?

Titration Problems
Ø 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 molar
concentration of the HCl.
Ø Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol)
required 43.31 mL of KMnO4. What is the molar
concentration of the KMnO4 solution? The chemical
reaction is

Titration Curves
Ø Titration curves are plots of a concentration-
related variable as a function of reagent volume.
Ø 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.

Titration Curves
Ø Types of Titration
curves
ü A sigmoidal curve,
important
observations are
confined to a small
region (typically ±
0.1 to ± 0.5 mL)
surrounding the
equivalence point.

Titration Curves
Ø Types of Titration
curves
ü Linear segment curve,
measurements are
made on both sides of
but well away from
the equivalence point.
Measurements near
equivalence are
avoided.

Titration Curves
ü Titration curves
of pH and pOH
versus volume of
base for the
titration of
0.1000 M HCl
with 0.1000 M
NaOH.

Acid and Base Titration: Neutralization
Ø Widely used to determine the amount of acid
and bases
Ø Can be used to monitor the progress of
reactions that produce or consume hydrogen
ions
Ø Standard Solutions
ü Always strong acids or strong bases such as HCl,
HClO4, H2SO4, NaOH, and KOH.
ü Weak acids and bases are never used as standard
reagents because they react incompletely with
analytes.
Ø Acid/Base Indicators
ü It 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.
ü Acid-type indicator reaction
ü Base-type indicator reaction

Ø Acid/Base
Indicators
ü Structural
change in
phenolphthalein

ü The pH transition range of most acid type
indicators is



Ø Equivalence point
ü The point in a titration where stoichiometrically
equivalent amounts of analyte and titrant react.
ü The pH depends on the salt formed
q Strong Acid + Strong base: pH = 7.00
q Strong acid + weak base: pH < 7.00

Ø Titration of Strong Acid with Strong Base
ü Stages and calculations
q Initial Point – The hydronium ions in an
aqueous solution of a strong acid have two
sources: (1) the reaction of the acid with water
and (2) the dissociation of water itself. In all but
the most dilute solutions, however, the
contribution from the strong acid far exceeds
that from the solvent.
q Pre-equivalence point - concentration of the acid
is computed from its starting concentration and
the amount of base added.
q Equivalence Point - the hydronium and
hydroxide ions are present in equal
concentrations, and the hydronium ion con-
centration can be calculated directly from the
ion-product constant for water, Kw.
q Post-equivalence point - 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.
ü Titration Curve for
HCl and NaOH
v 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
0.00100 M NaOH.
v Curve A (higher
concentration of titrant
has sharper end point
than Curve B (lower
concentration)
ü Problem (Example 14-1): Generate the
hypothetical titration curve for the titration of
50.00 mL of 0.0500 M HCl with 0.1000 M
NaOH at 250C.

Ø Titration of Strong Base with Strong Acid
v Initial point – basic
v Pre-equivalence point – hydroxide ion
concentration is computed from the amount
remaining in the solution
v Equivalence point – neutral
v Post-equivalence point – excess acid is
present

Ø Titration of Strong Base with Strong Acid
ü Titration Curve

Ø Titration of Weak Acids and Bases with Strong
ü Stages
v Initial point – the solution contains only a
weak acid or a weak base
q pH is calculated from the concentration of
that solute and its dissociation constant.

ü Stages
v Pre-equivalence point - the solution consists
of a series of buffers.
q 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
q May use Henderson-Hasselbach equation:
pH = pK a + log
[ salt ]
[acid ]
ü Stages
v Equivalence point - the solution contains only
the conjugate of the weak acid or base being
titrated (salt)
q The pH is calculated from the concentration
of this product

ü Stages
v Post-equivalence point - the solution contains
the excess of strong acid or base titrant
q The pH is calculated from the concentration
of the excess titrant

ü Titration Curve of
acetic acid with
NaOH
v Curve A: 0.1000 M
acid with
0.1000 M base.
v Curve B: 0.001000
M acid with
0.001000 M base.

ü Problem (Example 14-3). Generate a curve for
the titration of 50.00 mL of 0.1000 M acetic acid
(HOAc) with 0.1000 M sodium hydroxide at
250C.

Ø Titration of Mixture of Strong and Weak Acids
or Strong and Weak Bases
ü Each of the components in a mixture containing
a strong acid and a weak acid (or a strong base
and a weak base) can be determined provided
that the concentrations of the two are of the same
order of magnitude and that the dissociation
constant for the weak acid or base is somewhat
less than about 10-4.

References
ü Harris, D. (2007). Quantitative Chemical Analysis, 8th ed.,
Freeman, NY.
ü Harvey, D. (2000). Modern Analytical Chemistry, McGraw-
Hill, US.
ü Skoog D. A. et al. (2013)Fundamentals of Analytical
Chemistry, Cengage Learning.
ü Chang (2013). Chemistry, 10th ed.
ü Moore, Stanitski, Jurs (2008). Chemistry: The Molecular
Science
ü Whitten, Davis, Peck and Stanley (2013). Chemistry, 9th ed.

Volumetric Analysis: Dr. Kathlia A. de Castro-Cruz Analytical Chemistry 1

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Volumetric Analysis

Dr. Kathlia A. De Castro-Cruz

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Potassium hydrogen phthalate COOH

Potassium hydrogen iodate KH(IO3)2 389.912

Benzoic acid COOH

Sulfamic acid H3N+SO3- 97.094

Sodium tetraborate decahydrate

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ü Base-type indicator reaction

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