TITRIMETRIC METHOD Merged Compressed Merged

TITRIMETRIC METHODS
Dr Ha Minh Hien
TITRIMETRIC METHOD
INTRODUCTION
 Titrimetric method of analysis
is a quantitative analysis, in
which volume serves as the
analytical signal.
 The volume of a solution with
known concentration is
accurately measured upon
completely reacting with the
(Louis – Joseph GAY – LUSSAC)
1778 – 1850. analyte (s) of interest.
TITRIMETRIC METHOD
INTRODUCTION
 Titrimetric methods were not well received by the analytical
chemists of that era because they could not duplicate the
accuracy and precision of a gravimetric analysis. Not
surprisingly, few standard texts from that era include titrimetric
methods of analysis.
 Unlike gravimetry, the development and acceptance of titrimetry
required a deeper understanding of stoichiometry, of
thermodynamics, and of chemical equilibria. By the 1900s, the
accuracy and precision of titrimetric methods were comparable
to that of gravimetric methods, establishing titrimetry as an
accepted analytical technique.
Flash review
 Stoichiometry refers to the relationship between the quantities

of reactants and products before, during, and following chemical
reactions.
 Stoichiometry is founded on the law of conservation of mass where the
total mass of the reactants equals the total mass of the products, leading
to the insight that the relations among quantities of reactants and
products typically form a ratio of positive integers.
 This means that if the amounts of the separate reactants are known,
then the amount of the product can be calculated.
 Conversely, if one reactant has a known quantity and the quantity of the
products can be empirically determined, then the amount of the other
reactants can also be calculated.
 Here, one molecule of methane reacts with two molecules
of oxygen gas to yield one molecule of carbon dioxide and two
molecules of water.
 This particular chemical equation is an example of complete
combustion. Stoichiometry measures these quantitative relationships,
and is used to determine the amount of products and reactants that are
produced or needed in a given reaction.
 Describing the quantitative relationships among substances as they
participate in chemical reactions is known as reaction stoichiometry.
 In the example above, reaction stoichiometry measures the relationship
between the quantities of methane and oxygen that react to form
carbon dioxide and water.
 Because of the well known relationship of moles to atomic weights, the
ratios that are arrived at by stoichiometry can be used to determine
quantities by weight in a reaction described by a balanced equation.
This is called composition stoichiometry.
OVERVIEW OF TITRIMETRY
 In titrimetry we add a reagent, called the TITRANT, to a
solution that contains another reagent, called the TITRAND,
and allow them to react.
 The type of reaction provides us with a simple way to divide
titrimetry into four categories: acid–base titrations, in which
an acidic or basic titrant reacts with a titrand that is a base or
an acid; complexometric titrations, which are based on metal–
ligand complexation; redox titrations, in which the titrant is an
oxidizing or reducing agent; and precipitation titrations, in
which the titrand and titrant form a precipitate.
 Despite their difference in chemistry, all titrations share
several common features.
 Before we consider individual titrimetric methods in greater
detail, let’s take a moment to consider some of these
similarities.
 This overview will help you focus on the similarities between
different titrimetric methods.
 It easier to understand a new analytical method when you
can see its relationship to other similar methods.
 If a titration is to give an accurate result we must combine the titrand and
the titrant in stoichiometrically equivalent amounts. We call this
stoichiometric mixture the EQUIVALENCE POINT.
 An accurate titration requires that we know the exact volume of titrant at
the equivalence point, Veq. The product of the titrant’s equivalence point
volume and its molarity, MT, is equal to the moles of titrant that react with
the titrand.
moles titrant = MT x Veq
 If we know the stoichiometry of the titration reaction, then we can calculate
the moles of titrand.
Example:
NaCl + AgNO3  AgCl + NaNO3
1 mole 1 mole
 Unfortunately, for most titration reactions there is no obvious sign
when we reach the equivalence point.
 Instead, we stop adding the titrant at an END POINT of our
choosing. Often this end point is a change in the color of a
substance, called an INDICATOR, that we add to the titrand’s
solution.
 The difference between the end point’s volume and the equivalence
point’s volume is a determinate TITRATION ERROR.
 If the end point and the equivalence point volumes coincide closely,
then this error is insignificant and is safely ignored. Clearly,
selecting an appropriate end point is of critical importance.
 Almost any chemical reaction can serve as a titrimetric method provided
that it meets the following four conditions. The first condition is that we
must know the stoichiometry between the titrant and the titrand. If this
is not the case, then we cannot convert the moles of titrant used to
reach the end point to the moles of titrand in our sample.
 Second, the titration reaction effectively must proceed to completion;
that is, the stoichiometric mixing of the titrant and the titrand must
result in their complete reaction.
 Third, the titration reaction must occur rapidly. If we add the titrant
faster than it can react with the titrand, then the end point and the
equivalence point will differ significantly.
 Finally, we must have a suitable method for accurately determining the
end point. These are significant limitations and, for this reason, there
are several common titration strategies.
 A simple example of a titration is an analysis for Ag+ using
thiocyanate, SCN–, as a titrant.
Ag+ (aq) + SCN- (aq) AgSCN (s)
 This reaction occurs quickly and with a known stoichiometry, which
satisfies two of our requirements.
 To indicate the titration’s end point, we add a small amount of Fe3+
to the analyte’s solution before we begin the titration.
 When the reaction between Ag+ and SCN– is complete, formation of
the red-colored Fe(SCN)2+ complex signals the end point. This is an
example of a DIRECT TITRATION since the titrant reacts directly
with the analyte.
 If the titration’s reaction is too slow, if a suitable indicator is not available, or
if there is no useful direct titration reaction, then an indirect analysis may be
possible.
 Suppose you wish to determine the concentration of formaldehyde, H2CO, in
an aqueous solution. The oxidation of H2CO by I3- is a useful reaction, but it
is too slow for a titration.
H2CO (aq) + I3- (aq) + 3OH- (aq) HCO2- (aq) + 3I- (aq) + 2H2O (l)
 If we add a known excess of I3- and allow its reaction with H2CO to go to
completion, we can titrate the unreacted I3- with thiosulfate, S2O32-.
I3- (aq) + 2S2O32- (aq) S4O62- (aq) + 3I- (aq)
 The difference between the initial amount of I3- and the amount in excess
gives us the amount of I3- that reacts with the formaldehyde. This is an
example of a BACK TITRATION.
 Calcium ions play an important role in many environmental systems. A direct
analysis for Ca2+ might take advantage of its reaction with the ligand
ethylenediaminetetraacetic acid (EDTA), which we represent here as Y4–.
Ca2+ (aq) + Y4- (aq) CaY2- (aq)
 Unfortunately, for most samples this titration does not have a useful indicator.
Instead, we react the Ca2+ with an excess of MgY2 releasing an amount of Mg2+
equivalent to the amount of Ca2+ in the sample.
Ca2+ (aq) +MgY2- (aq) CaY2- (aq) + Mg2+ (aq)
 Because the titration of Mg2+ with EDTA has a suitable end point, we can
complete the analysis. The amount of EDTA used in the titration provides an
indirect measure of the amount of Ca2+ in the original sample. Because the
species we are titrating was displaced by the analyte, we call this a
DISPLACEMENT TITRATION.
Mg2+ (aq) + Y4- (aq) MgY2- (aq)
 If a suitable reaction with the analyte does not exist it may be

possible to generate a species that we can titrate.
 For example, we can determine the sulfur content of coal by using
a combustion reaction to convert sulfur to sulfur dioxide
S (s) + O2 (g) SO2 (g)
 and then convert the SO2 to sulfuric acid, H2SO4, by bubbling it
through an aqueous solution of hydrogen peroxide, H2O2.
SO2 (g) + H2O2 (aq) H2SO4 (aq)
 Titrating H2SO4 with NaOH provides an indirect determination of
sulfur.
H2SO4 (aq) + 2NaOH (aq) 2H2O (l) + Na2SO4 (aq)
Titration curves
Example:
 Titration of HCl solution as titrand with NaOH solution as titrant using
phenolphthalein solution as indicator, the equivalence point occurs at a
pH of 7.0.
 A simple method for finding the equivalence point is to monitor the
titration mixture’s pH using a pH electrode, stopping the titration when
we reach a pH of 7.0. Alternatively, we can add an indicator to the
titrand’s solution that changes color at a pH of 7.0.
 Suppose the only available indicator changes color at a pH of 6.8. Is the
difference between this end point and the equivalence point small
enough that we safely can ignore the titration error? To answer this
question we need to know how the pH changes during the titration.
Titration curves
 A TITRATION CURVE provides a visual picture of how a
property of the titration reaction changes as we add the
titrant to the titrand.
 The titration curve was obtained by suspending a pH
electrode in a solution of 0.100 M HCl (the titrand) and
monitoring the pH while adding 0.100 M NaOH (the titrant).
 A close examination of this titration curve should convince
you that an end point pH of 6.8 produces a negligible
titration error. Selecting a pH of 11.6 as the end point,
however, produces an unacceptably large titration error.
Figure 1. Typical acid–base titration
curve showing how the titrand’s pH
changes with the addition of titrant.
The titrand is a 25.0 mL solution of
0.100 M HCl and the titrant is 0.100 M
NaOH. The titration curve is the solid
blue line, and the equivalence point
volume (25.0 mL) and pH (7.00) are
shown by the dashed red lines. The
green dots show two end points. The
end point at a pH of 6.8 has a small
titration error, and the end point at a
pH of 11.6 has a larger titration error.
 Other parameters, such as the temperature or absorbance of the titrand’s solution,
may provide a useful end point signal.
 Many acid–base titration reactions, for example, are exothermic. As the titrant and
the titrand react, the temperature of the titrand’s solution increases.
 Once we reach the equivalence point, further additions of titrant do not produce as
exothermic a response.
 Figure 2. shows a typical THERMOMETRIC TITRATION CURVE where the
intersection of the two linear segments indicates the equivalence point.
Figure 2. Example of a thermometric

titration curve showing the location of
the equivalence point.
(a) (b) (c)
Figure 3. Additional examples of titration curves.

(a) Complexation titration of 25.0 mL of 1.0 mM Cd2+ with 1.0 mM EDTA at a pH of
10. The y-axis displays the titrand’s equilibrium concentration as pCd.
(b) Redox titration of 25.0 mL of 0.050 M Fe2+ with 0.050 M Ce4+ in 1 M HClO4. The y-
axis displays the titration mixture’s electrochemical potential, E, which, through the
Nernst equation is a logarithmic function of concentrations.
(c) Precipitation titration of 25.0 mL of 0.10 M NaCl with 0.10 M AgNO3. The y-axis
displays the titrant’s equilibrium concentration as pAg.
OVERVIEW OF TITRIMETRY- Buret
 The most common method for delivering titrant is a buret, which is a
long, narrow tube with graduated markings and equipped with a
stopcock for dispensing the titrant.
 The buret’s small internal diameter provides a better defined
meniscus, making it easier to read precisely the titrant’s volume.
 Burets are available in a variety of sizes and tolerances (Table 9.1),
with the choice of buret determined by the needs of the analysis.
 You can improve a buret’s accuracy by calibrating it over several
intermediate ranges of volumes using the method for calibrating
pipets. Calibrating a buret corrects for variations in the buret’s
internal diameter.
 An automated titration uses a pump to deliver the titrant at a
constant flow rate (Figure 9.5).
 Automated titrations offer the additional advantage of using a
microcomputer for data storage and analysis.
OVERVIEW OF TITRIMETRY- Buret
Figure 4. A typical volumetric buret. The stopcock is shown here in the open
position, which allows the titrant to flow into the titrand’s solution. Rotating
the stopcock controls the titrant’s flow rate.
OVERVIEW OF TITRIMETRY-PRIMARY STANDARD
The materials, after drying under the specified conditions, are recommended
for use as primary standards in the standardisation of volumetric
solutions. Analytical reagent grade materials of commerce must be used.
Condition:
 High purity (> 99,95%).
 Air-stable.
 Large molecular weight.
 Not hygroscopic.
Example:
- Potassium hydrogen phthalate (KHP) C8H5O4K (M= 204.22 ). Dry at
105 oC and use for standardization of base with phenolphthalein as
indicator
- Potassium bicarbonate (KHCO3) (M= 100.11 g).
- Benzoic acid C6H5COOH (M= 122,15 g).
SECONDARY STANDARD
 Purity is determined by chemical analysis
̣ Its purity is lower than that of primary standard
 Example:
- Sodium borate, decahydrate Na2B4O7.10 H2O (M= 381.24).
Before preparation of volumeric solution, dry at 170 – 440 oC
for 1 h.
- Oxalic acid, H2C2O4. 2H2O (M= 252 g).
VOLUMETRIC SOLUTION (TITRANT)
 Volumetric solutions are prepared according to the usual chemical
analytical methods. The accuracy of the apparatus used is verified to
ensure that it is appropriate for the intended use.
 The concentration of volumetric solutions is indicated in terms of
molarity (M ). The molarity of a solution is the number of moles of
substance contained in 1000 mL of the solution. A solution that
contains x moles of substance per litre is said to be xM .
 Volumetric solutions do not differ from the prescribed strength by more
than 10%. The molarity of the volumetric solutions is determined by
an appropriate number of titrations. The repeatability does not exceed
0.2% (relative standard deviation).
Determination of concentration of standard
solution
The standard solution is used to react with the analyte, and
all stoichiometric calculations are dependent on the accurate
measurement of the volume of standard solution reacted.
Standard solutions are prepared in two ways:
 Direct method: a primary standard compound is carefully
weighed and dissolved in an exactly known volume of
solution. The direct method is the best method to utilized.
Determination of concentration of standard
solution
 Standardization (most of the titrants): the prepared
standard solution is standardized by using it to titrate
 A carefully weighed primary standard compound.
 A carefully weighed secondary standard compound
 A carefully measured volume of another standard
solution.
CATEGORY OF TITRIMETRIC METHODS
1. Acid-base titrations:
For quantitative analysis of acid, base and some salts in
aqueous or non-aqueous solvent. The method is based on
proton exchange of H+
HCl + NaOH NaCl + H2O
2. Redox titrations: on the basis of a redox reaction, in
which the titrant is an oxidizing or reducing agent
2FeCl3 + SnCl2 2FeCl2 + SnCl4
CATEGORY OF TITRIMETRIC METHODS
3. Precipitation titrations:
On the basis of reaction of analyte(s) with titrant to form a
precipitate
Ag+ + Cl- AgCl
4. Complexometric titrations:
On the basis of complex forming. It is commonly used for
quantitative analysis of metal ions such as Ca2+ and Mg2+ in
water with EDTA as titrant
Ca2+ + HY3- CaY2- + H+
MEASURING THE END POINT OF A TITRATION
Different methods for determination the endpoint include:
1. Indicator:
A substance that changes color in response to a chemical change. An acid–
base indicator (e.g., phenolphthalein) changes color depending on the
pH. Redox indicators are also used. A drop of indicator solution is added to
the titration at the beginning; the endpoint has been reached when the color
changes.
2. Potentiometer:
An instrument that measures the electrode potential of the solution. These
are used for redox titrations; the potential of the working electrode will
suddenly change as the endpoint is reached.
3. pH meter:
A potentiometer with an electrode whose potential depends on the amount
of H+ ion present in the solution. (This is an example of an ion-selective
electrode.) The pH of the solution is measured throughout the titration, more
accurately than with an indicator; at the endpoint there will be a sudden
change in the measured pH.
4. Conductivity:
A measurement of ions in a solution. Ion concentration can change
significantly in a titration, which changes the conductivity. (For instance,
during an acid–base titration, the H+ and OH− ions react to form neutral
H2O.) As total conductance depends on all ions present in the solution and
not all ions contribute equally (due to mobility and ionic strength), predicting
the change in conductivity is more difficult than measuring it.
5. Color change:
In some reactions, the solution changes color without any added indicator.
This is often seen in redox titrations when the different oxidation states of
the product and reactant produce different colors.
6. Precipitation:
If a reaction produces a solid, a precipitate will form during the titration. A
classic example is the reaction between Ag+ and Cl− to form the insoluble
salt AgCl. Cloudy precipitates usually make it difficult to determine the
endpoint precisely. To compensate, precipitation titrations often have to be
done as "back" titrations (see below).
7. Spectroscopy:
Used to measure the absorption of light by the solution during titration if
the spectrum of the reactant, titrant or product is known. The
concentration of the material can be determined by Beer's Law.
8. Amperometry:
Measures the current produced by the titration reaction as a result of the
oxidation or reduction of the analyte. The endpoint is detected as a
change in the current. This method is most useful when the excess titrant
can be reduced, as in the titration of halides with Ag+.
Indicators
 Indicators, the colours of which change over approximately the same
range of pH, may be substituted for one another but in the event of
doubt or dispute as to the equivalence of indicators for a particular
purpose, the indicator specified in the text is alone authoritative.
 The quantity of an indicator solution appropriate for use in acid-base
titrations described in assays or tests is 0.1 mL unless otherwise
stated in the text.
 Any solvent required in an assay or test in which an indicator is
specified is previously neutralised to the indicator, unless a blank test
is prescribed.
MULTIPLE CHOICE
QUESTION
1. Titrimetric method of analysis is a quantitative

analysisis in which …… serves as the analytical
signal.
a. Mass of titrant
b. Volume of titrant
c. Mass of primary standard
d. Mass of secondary standard
MULTIPLE CHOICE
QUESTION
2. Almost any chemical reaction can serve as a titrimetric method
provided that it meets the following conditions:
a. The stoichiometry defined, complete reaction, reaction must occur

rapidly, the end point accurately determined.
b. The titrant is air-stable, complete reaction, reaction must occur rapidly,

the end point accurately determined.
c. The titrant is air-stable, complete reaction, reaction must occur rapidly,

the equivalence point accurately determined.
d. The titrant is air-stable, complete reaction, reaction must occur

moderately, the end point accurately determined.
MULTIPLE CHOICE QUESTION
3. Titration is performed by adding the…..to a titrand and allow
them to react:
a. Titrant
b. Primary standard
c. Secondary standard
d. Reagent
4. Characteristics of volumetric solution are:
a. Stable, having a specific formula
b. Non-hydroscopic, large molecular weight
c. Having a specific conconcentration, stable, rapid reaction, complete
reaction and reacting with titrand selectively
d. Stable, rapid reaction, complete reaction and reacting with titrand
selectively, having a specific conconcentration, less time consuming for
preparation, low cost, simple technique
5. Which of the following glassware is uesd to measure volume of

a solution accurately?
a. Becher
b. Graduated cylinder
c. Buret
d. Graduated pipette
6. For accurately determination of the equivalence point, one can

use: Hiện nay để phát hiện điểm tương đương một cách chính
xác nhất, người ta dựa vào?
a. A mixture of two indicators
b. Internal indicator
c. External indicator
d. Physicochemical methods
7. Equivalence point is:?
a. The point at which the titrand and the titrant is in stoichiometrically
equivalent amounts.
b. The point at which the volume of reagent is needed for the titration
c. The point at which the indicator changes colour.
d. The point at which the error is free
8. Indicator is:
a. An amphoteric substance
b. Substance whose colour is easy to recognize at equivalence point
c. Substances that are able to change their colour or generate any signal
at about the equivalence point
d. Cation
ACID – BASE TITRATION
Dr Ha Minh Hien
REVIEW
Acid: accepts pair of electron Acid: a proton (H+) donor

Base: donates pair of electron Base: a proton acceptor
Bronsted-Lowry acid-base theory
Acid: HCl Cl- + H+ HCl/Cl-: acid-conjugate base
Base: NH3 + H+ NH4+ NH3/ NH4 +: base-conjugate acid
Acid Base
NH4+ CH3COOH HCO3- NH3 CH3COO- CO32-
Acid and base could be molecule as well as ion

Reaction of acid-base with solvent as per
Bronsted theory
(Solvent with activated proton)
∙ Water as solvent could be an acid or base

∙ Water is an acid: H2O ↔ OH- + H+
∙ Water is a base: H2O + H+ ↔ H3O+ (Hydronium ion)
∙ Formamide as solvent could be an acid or base

∙ Formamide is an acid: HCONH2 ↔ HCONH- + H+
∙ Formamide is a base: HCONH + H+ ↔ HCONH3+
∙ Alcohol as solvent could be an acid or base

∙ Alcohol is an acid: ROH ↔ RO- + H+
∙ Alcohol is a base: ROH + H+ ↔ ROH2+
Reaction of acid-base with solvent as per
Bronsted theory
(Solvent with activated proton)
∙ H+ does not exist in a free form

∙ There is a pair of donors and a pair of acceptors
∙ HF + H2O ↔ F- + H3O+
∙ HF and H3O: H+ donor
∙ H2O and F-: H+ acceptor
∙ NH4+ + H2O ↔ NH3 + H3O+

∙ NH4+ and H3O+ : H+ donor
∙ H2O and NH3 : H+ acceptor
DISSOCIATION OF AMPHOTERIC PROTIC SOLVENT
SH: solvent with active H+ (S; Solvent)
SH + SH ↔ S- + SH2+
2H2O ↔ H3O+ + OH-
[SH] or [H2O]: constant (very few molecules dissociate)

[S-] [SH2+] = K [SH]2 = Ki (ionization constant)
At 23 oC, the ionization constant of water,Kw
[OH-] [H3O+] = 10-14
Acid/Base strength in amphoteric protic solvent
Acid
HA + SH ↔ A- + SH2+
pKa = -lgKa
pKa: constant
∙ Ka ↑ ⇒ Acid strength ↑
∙ Ka ↑ ⇒ pKa ↓
∙ pKa to determine the strength of a pair of acid/base
Acid/Base strength in amphoteric protic solvent
Base
B + SH ↔ S- + BH+
[S-] [SH2+] = Ki
Ka x K b = K i
∙ pKa to determine the strength of a pair of acid/base
Acid and base strength
❑ Strong acid: acid that ionizes rapidly and almost completely

in water; acid with pKa < 0
Examples: HCl, HB, HI, HClO3, HNO3, HClO4, H2SO4
❑ Weak Acid: acid that partially dissociates in water; acid with
pKa > 0 such as CH3COOH
❑ Strong base: base that dissociates completely into water;
strong base with pKa > 0 such as: NaOH, LiOH, KOH
❑ Weak Base: base that partially dissociates in water; base
with pKa < 0 such as NH3
Henderson–Hasselbalch equation
Solvent: water or amphoteric protic solvent

BUFFER SOLUTION
❑ An aqueous solution consisting of a mixture of a weak acid and
its conjugate base*, or vice versa.
❑ Its pH changes very little when a small amount of strong acid or base is
added to it.
❑ Buffer solutions are used as a means of keeping pH at a nearly constant
value
∙ A conjugate acid, within the Bronsted–Lowry acid–base theory, is a

chemical compound formed when an acid donates a proton (H+) to
a base (it is a base with a hydrogen ion added to it)
∙ *A conjugate base is what is left over after an acid has donated a
proton during a chemical reaction (a species formed by the removal of a
proton from an acid.)
INTRODUCTION
∙ Before 1800, most acid–base titrations used H 2SO4, HCl, or
HNO3 as acidic titrants, and K2CO3 or Na2CO3 as basic titrants.
∙ A titration’s endpoint was determined using litmus as an
indicator, which is red in acidic solutions and blue in basic
solutions, or by the cessation of CO2 effervescence when
neutralizing CO32-.
∙ Early examples of acid–base titrimetry include determining
the acidity or alkalinity of solutions, and determining the
purity of carbonates and alkaline earth oxides.
INTRODUCTION
∙ Three limitations slowed the development of acid–base titrimetry:

▪ the lack of a strong base titrant for the analysis of weak acids,
▪ the lack of suitable indicators,
▪ and the absence of a theory of acid–base reactivity.
∙ The introduction, in 1846, of NaOH as a strong base titrant
extended acid–base titrimetry to the determination of weak acids.
∙ The synthesis of organic dyes provided many new indicators.
∙ Phenolphthalein, for example, was first synthesized by Bayer in
1871 and used as an indicator for acid–base titrations in 1877.
INTRODUCTION
∙ Despite the increased availability of indicators, the absence of a theory of
acid–base reactivity made it difficult to select an indicator.
∙ The development of equilibrium theory in the late 19th century led to
significant improvements in the theoretical understanding of acid–base
chemistry, and, in turn, of acid–base titrimetry.
∙ Sørenson’s establishment of the pH scale in 1909 provided a rigorous
means to compare indicators.
∙ The determination of acid–base dissociation constants made it possible to
calculate a theoretical titration curve, as outlined by Bjerrum in 1914.
∙ For the first time analytical chemists had a rational method for selecting
an indicator, making acid–base titrimetry a useful alternative to
gravimetry.
❑ Neutralization is a chemical reaction in which acid and

a base react quantitatively with each other.
❑ Equivalence point is
determined by observation
the change in acid or base
concentration when it
approaches the
neutralization
Method for finding the end point with an indicator
Indicator: substance
spiked into solution for
identification of the end
point upon the colour
change occurs.
Mechanism of indicator’s
colour change:
Structure of indicator
electronically changed by
acceptance or donate a
proton H+ or a hydroxyl
group OH-
∙ Let’s consider an indicator for which the acid form, HIn, is yellow and
the base form, In–, is red.
∙ The color of the indicator’s solution depends on the relative
concentrations of HIn and In–.
∙ To understand the relationship between pH and color we use the
indicator’s acid dissociation reaction.
and its equilibrium constant expression.

∙ Taking the negative log of each side of equation for K a, and rearranging to solve
for pH leaves us with a equation that relates the solution’s pH to the relative
concentrations of HIn and In–.
∙ If we can detect HIn and In– with equal ease, then the transition from
yellow-to-red (or from red-to-yellow) reaches its midpoint, which is orange, when
the concentrations of HIn and In– are equal, or when the pH is equal to the
indicator’s pKa.
∙ If the indicator’s pKa and the pH at the equivalence point are identical, then
titrating until the indicator turns orange is a suitable end point.
∙ Unfortunately, we rarely know the exact pH at the equivalence point. In addition,
determining when the concentrations of HIn and In– are equal is difficult if the
indicator’s change in color is subtle.
∙ We can establish the range of pHs over which the average analyst observes a
change in the indicator’s color by making two assumptions: that the
indicator’s color is yellow if the concentration of HIn is 10× greater than that
of In–.
∙ and that its color is red if the concentration of HIn is 10× smaller than that of
In–.
∙ Substituting these inequalities into the equation below:
shows that the indicator changes color over a pH range that extends ±1 unit on
either side of its pKa.
Figure 1 Diagram showing the
relationship between pH and an
indicator’s color. The ladder diagram
defines pH values where HIn and In– are
the predominate species. The indicator
changes color when the pH is between
pKa – 1 and pKa + 1.
∙ The indicator is yellow when the pH is less than pKa – 1

∙ and it is red when the pH is greater than pKa + 1.
∙ For pH values between pKa – 1 and pKa + 1 the indicator’s color
passes through various shades of orange.
Properties of Selected Acid–Base Indicators
∙ The relatively broad range of pHs over which an indicator changes color
places additional limitations on its ability to signal a titration’s end point.
∙ To minimize a determinate titration error, the indicator’s entire pH range
must fall within the rapid change in pH near the equivalence point.
∙ For example, phenolphthalein is an appropriate indicator for the titration
of 50.0 mL of 0.050 M acetic acid with 0.10 M NaOH.
∙ Bromothymol blue, on the other hand, is an inappropriate indicator
because its change in color begins well before the initial sharp rise in
pH, and, as a result, spans a relatively large range of volumes.
∙ The early change in color increases the probability of obtaining an
inaccurate result, and the range of possible end point volumes increases
the probability of obtaining imprecise results.
Figure 2 Portion of the titration curve for 50.0 mL of 0.050 M CH 3COOH with
0.10 M NaOH, highlighting the region that contains the equivalence point. The
end point transitions for the indicators phenolphthalein and bromothymol blue are
superimposed on the titration curve.
Titrating Strong Acids and Strong Bases
Step 1: Calculate the volume of titrant needed to reach the equivalence
point.
∙ Let’s consider the titration of 50.0 mL of 0.100 M HCl using a titrant of
0.200 M NaOH.
∙ When a strong base and a strong acid react the only reaction of
importance is
H3O+ (aq) + OH- (aq) → 2H2O (l)
Calculate the volume of NaOH needed to reach the equivalence point, Veq.
∙ At the equivalence point from reaction above:
moles HCl = moles NaOH
Ma x V a = M b x V b
where the subscript ‘a’ indicates the acid, HCl, and the subscript ‘b’ indicates
the base, NaOH.
∙ The volume of NaOH needed to reach the equivalence point is

Step 2: Calculate pH values before the equivalence point by determining
the concentration of unreacted titrand.
∙ Before the equivalence point, HCl is present in excess and the pH is

determined by the concentration of unreacted HCl.
∙ At the start of the titration the solution is 0.100 M in HCl, which, because
HCl is a strong acid, means the pH is
∙ After adding 10.0 mL of NaOH the concentration of excess HCl is
pH = –log(0.0500) = 1.30
Step 3: The pH at the equivalence point for the titration of a strong acid
with a strong base is 7.00.
∙ At the equivalence point the moles of HCl and the moles of NaOH are equal.
∙ Since neither the acid nor the base is in excess, the pH is determined by the
dissociation of water.
∙ The pH at the equivalence point is 7.00.

∙ For volumes of NaOH greater than the equivalence point, the pH is
determined by the concentration of excess OH–.
∙ For example, after adding 30.0 mL of titrant the concentration of OH– is
Step 4: Calculate pH values after the equivalence point by

determining the concentration of excess titrant.
∙ To find the concentration of H3O+ we use the Kw

expression
∙ To find that the pH is 12.10. Table 1 and Figure 1 show

additional results for this titration curve.
∙ Using this same approach to calculate the titration curve for
the titration of a strong base with a strong acid, except the
strong base is in excess before the equivalence point and
the strong acid is in excess after the equivalence point.
Table 1 Titrating Strong Acids and Strong Bases
Figure 3 Titration curve for the

titration of 50.0 mL of 0.100 M HCl
with 0.200 M NaOH. The red
points correspond to the data in
Table above. The blue line shows
the complete titration curve.
Titrating a weak acid with a strong base
Step 1: Calculate the volume of titrant needed to reach the equivalence
point.
∙ Let’s consider the titration of 50.0 mL of 0.100 M acetic acid, CH3COOH,

with 0.200 M NaOH.
∙ Start by calculating the volume of NaOH needed to reach the equivalence
point; thus
Step 2: Before adding the titrant, the pH is determined by the titrand,
which in this case is a weak acid.
∙ Before beginning the titration the pH is that for a solution of 0.100 M acetic
acid.
∙ Because acetic acid is a weak acid, calculate the pH as follows
∙ The pH is 2.88
Ka: acid dissociation constant
*A weak acid, of which aqueous acetic acid is one example, does not completely
donate its acidic proton to the solvent. Instead, most of the acid remains
undissociated with only a small fraction present as the conjugate base.
Step 3: Before the equivalence point, the pH is determined by a buffer that
contains the titrand and its conjugate form.
∙ Adding NaOH converts a portion of the acetic acid to its conjugate base,
CH3COO–.
∙ Because the equilibrium constant for reaction is quite large
K = Ka/Kw = 1.75 × 109
we can treat the reaction as if it goes to completion.
∙ Any solution that contains comparable amounts of a weak acid, HA, and
its conjugate weak base, A–, is a buffer.
∙ We can calculate the pH of a buffer using the Henderson–Hasselbalch
equation.
Before the equivalence point the concentration of unreacted acetic acid is
and the concentration of acetate is
For example, after adding 10.0 mL of NaOH the concentrations of

CH3COOH and CH3COO– are
which gives us a pH of
Step 4: The pH at the equivalence point is determined by the titrand’s
conjugate form, which in this case is a weak base.
∙ At the equivalence point the moles of acetic acid initially present and the
moles of NaOH added are identical.
∙ Because their reaction effectively proceeds to completion, the
predominate ion in solution is CH3COO–, which is a weak base.
∙ To calculate the pH we first determine the concentration of CH3COO–
∙ Calculate the pH of the weak base
∙ Finding that the pH at the equivalence point is 8.79.

Step 5: Calculate pH values after the equivalence point by determining
the concentration of excess titrant.
∙ After the equivalence point, the titrant is in excess and the titration mixture is a
dilute solution of NaOH.
∙ We can calculate the pH using the same strategy as in the titration of a strong
acid with a strong base.
∙ For example, after adding 30.0 mL of NaOH the concentration of OH - is
∙ Giving a pH of 12.10.
Table 2 Titrating a weak acid with a strong base
Figure 4 Titration curve for the titration of

50.0 mL of 0.100 M CH3COOH with 0.200 M
NaOH. The red points correspond to the
data in Table 2. The blue line shows the
complete titration curve.
Polyprotic acid: specific acids Titration of polyprotic acid
that are capable of losing more
than a single proton per
molecule in acid-base reactions.
H2SO4: strong polyprotic acid

H3PO4: weak polyprotic acid
∙ In strong acid + strong base titrations, the pH changes slowly at first, rapidly
through the equivalence point of pH=7, and then slows down again. If it is
being titrated in a strong acid, the pH will go up as the base is added to it.
Conversely, if it is in a strong base, the pH will fall down as acid is added.
∙ In strong acid + weak base titrations, the pH changes slowly at the
equivalence point and the pH equals the pKa of the acid. The pH is below 7.
∙ For the weak acid + strong base, the pH is above 7 at the equivalence point.
Titration of polyprotic acid
❑ Sulphuric acid: this unique polyprotic
acid is the only one to be completely
deprotonated after the first step
❑ Phosphoric acid: three dissociation

reactions, three steps to fully remove
the H+ ion, 3 equivalence points.
pKa1 = 2.1 (H3PO4 H+ + H2PO4-)
pKa2 = 7.2 (H2PO4- H+ + HPO42-)
pKa3= 12.4 (HPO42- H+ + PO43-)

Condition:
❑ pKa1 – pKa2: ≥ 4
❑ Tartaric acid: pK1 = 2,5; pK2 = 4,2: not clearly define the equivalence point
Titrations in Nonaqueous Solvents
Analysis target:
Acid/base:
✔ High molecular weight
✔ Limited solubility in water
Organic compound of very weak acid/base (Ka or Kb < 10-8)
In nonaqueous solvent: acid/base improves its strength ⇒ Finding the
end point easily
For an amphoteric solvent, SH, the autoprotolysis constant, Ks, relates

the concentration of its protonated form, SH2+, to its deprotonated
form, S–
And the solvent’s pH and pOH are
∙ The most important limitation imposed by Ks is the change in pH during a

titration.
∙ Let’s consider the titration of 50.0 mL of 1.0×10–4 M HCl using 1.0×10–4 M
NaOH as the titrant.
∙ Before the equivalence point, the pH is determined by the untitrated
strong acid. For example, when the volume of NaOH is 90% of Veq, the
concentration of H3O+ is
and the pH is 5.3.

When the volume of NaOH is 110% of Veq, the concentration of OH– is
and the pOH is 5.3. The titrand’s pH is
and the change in the titrand’s pH as the titration goes from 90% to
110% of Veq is
∙ If we carry out the same titration in a nonaqueous amphiprotic
solvent that has a Ks of 1.0×10–20, the pH after adding 45.0 mL of
NaOH is still 5.3. However, the pH after adding 55.0 mL of NaOH is
∙ In this case the change in pH

is significantly greater than that
obtained when the titration is carried
out in water. (Figure 5)
Figure 5 Titration curves for 50.0 mL

of 1.0 × 10–4 M HCl using 1.0 × 10–4 M
NaOH in (a) water, Kw = 1.0 × 10–14,
and (b) a nonaqueous amphiprotic
solvent, Ks = 1.0 × 10–20
∙ Another parameter that affects the feasibility of an acid–base titration is
the titrand’s dissociation constant. Here, too, the solvent plays an
important role.
∙ The strength of an acid or a base is a relative measure of how easy it is
to transfer a proton from the acid to the solvent or from the solvent to
the base. For example, HF, with a Ka of 6.8 × 10–4, is a better proton
donor than CH3COOH, for which Ka is 1.75 × 10–5.
∙ The strongest acid that can exist in water is the hydronium ion, H3O+.
∙ HCl and HNO3 are strong acids because they are better proton donors
than H3O+ and essentially donate all their protons to H2O, leveling their
acid strength to that of H3O+.
∙ In a different solvent HCl and HNO3 may not behave as strong acids.
∙ If we place acetic acid in water the dissociation reaction
does not proceed to a significant extent because CH3COO– is a stronger

base than H2O and H3O+ is a stronger acid than CH3COOH.
∙ If we place acetic acid in a solvent that is a stronger base than water,
such as ammonia, then the reaction
proceeds to a greater extent. In fact, both HCl and CH3COOH are strong
acids in ammonia.
∙ All other things being equal,

∙ The strength of a weak acid increases if we place it in a solvent that is
more basic than water, and the strength of a weak base increases if
we place it in a solvent that is more acidic than water.
∙ In some cases, however, the opposite effect is observed. For example,
the pKb for NH3 is 4.75 in water and it is 6.40 in the more acidic glacial
acetic acid.
∙ In contradiction to our expectations, NH3 is a weaker base in the more
acidic solvent.
∙ A titration that is not feasible in water may be feasible in a different
solvent.
Selecting and Standardizing a Titrant
The most common strong acid titrants are HCl, HClO4, and H2SO4.
Solutions of these titrants usually are prepared by diluting a commercially
available concentrated stock solution.
Because the concentration of a concentrated acid is known only
approximately, the titrant’s concentration is determined by standardizing
against one of the primary standard weak bases listed in Table 3.
The most common strong base titrant is NaOH, which is available both as
an impure solid and as an approximately 50% w/v solution.
Solutions of NaOH are standardized against any of the primary weak acid
standards listed in Table 3.
Selected Primary Standards for Standardizing Strong Acid and
Table 3 Strong Base Titrants
a The end point for this titration is improved by titrating to the second equivalence point,
boiling the solution to expel CO2, and retitrating to the second equivalence point. The
reaction in this case is Na2CO3 + 2H3O+ → CO2 + 2Na+ + 3H2O
b Tris-(hydroxymethyl)aminomethane often goes by the shorter name of TRIS or THAM.
c Potassium hydrogen phthalate often goes by the shorter name of KHP.
d Because it is not very soluble in water, dissolve benzoic acid in a small amount of
ethanol before diluting with water.
Using NaOH as a titrant is complicated by potential contamination
from the following reaction between dissolved CO2 and OH–.
During the titration, NaOH reacts both with the titrand and with CO2,
which increases the volume of NaOH needed to reach the titration’s
end point.
This is not a problem if the end point pH is less than 6. Below this pH
the CO32- from the above reaction reacts with H3O+ to form carbonic
acid.
Combining the two reactions gives an overall reaction that does not
include OH–.
Under these conditions the presence of CO2 does not affect the quantity
of OH– used in the titration and is not a source of determinate error.
If the end point pH is between 6 and 10, however, the neutralization of
CO32- requires one proton
If the end point pH is between 6 and 10, however, the neutralization of
CO32- requires one proton
and the net reaction between CO2 and OH– is
Under these conditions some OH– is consumed in neutralizing CO2,

which results in a determinate error.
We can avoid the determinate error if we use the same end point pH for
both the standardization of NaOH and the analysis of our analyte,
although this is not always practical.
Solid NaOH is always contaminated with carbonate due to its contact with
the atmosphere, and we cannot use it to prepare a carbonate-free solution
of NaOH.
Solutions of carbonate-free NaOH are prepared from 50% w/v NaOH
because Na2CO3 is insoluble in concentrated NaOH.
When CO2 is absorbed, Na2CO3 precipitates and settles to the bottom of
the container, which allow access to the carbonate-free NaOH.
When preparing a solution of NaOH, be sure to use water that is free

from dissolved CO2.
Briefly boiling the water expels CO2; after it cools, the water is used to
prepare carbonate-free solutions of NaOH.
A solution of carbonate-free NaOH is relatively stable if we limit its
contact with the atmosphere.
Standard solutions of sodium hydroxide are not stored in glass bottles as
NaOH reacts with glass to form silicate;
Instead, store such solutions in polyethylene bottles.
Inorganic Analysis
Acid–base titrimetry is a standard method for the quantitative

analysis of many inorganic acids and bases.
A standard solution of NaOH is used to determine the concentration
of inorganic acids, such as H3PO4 or H3AsO4, and inorganic bases,
such as Na2CO3 are analyzed using a standard solution of HCl.
If an inorganic acid or base that is too weak to be analyzed by an
aqueous acid–base titration, it may be possible to complete the
analysis by adjusting the solvent or by an indirect analysis.
For example, when analyzing boric acid, H3BO3, by titrating with
NaOH, accuracy is limited by boric acid’s small acid dissociation
constant of 5.8 × 10–10.
Inorganic Analysis
Boric acid’s Ka value increases to 1.5 × 10–4 in the presence of

mannitol, because it forms a stable complex with the borate ion,
which results is a sharper end point and a more accurate titration.
Similarly, the analysis of ammonium salts is limited by the ammonium
ion’ small acid dissociation constant of 5.7 × 10–10.
We can determine NH4+ indirectly by using a strong base to convert it
to NH3, which is removed by distillation and titrated with HCl.
Because NH3 is a stronger weak base than NH4+ is a weak acid (its Kb
is 1.58× 10–5), the titration has a sharper end point.
Inorganic Analysis
We can analyze a neutral inorganic analyte if we can first convert it into
an acid or a base.
For example, we can determine the concentration of NO3- by reducing it
to NH3 in a strongly alkaline solution using Devarda’s alloy, a mixture of
50% w/w Cu, 45% w/w Al, and 5% w/w Zn.
The NH3 is removed by distillation and titrated with HCl.

Alternatively, we can titrate NO3- as a weak base by placing it in an
acidic nonaqueous solvent, such as anhydrous acetic acid, and using
HClO4 as a titrant.
Inorganic Analysis
Acid–base titrimetry continues to be listed as a standard method for the
determination of alkalinity, acidity, and free CO2 in waters and
wastewaters.
Alkalinity is a measure of a sample’s capacity to neutralize acids.
The most important sources of alkalinity are OH–, HCO3-, and CO32-,
although other weak bases, such as phosphate, may contribute to the
overall alkalinity.
Total alkalinity is determined by titrating to a fixed end point pH of 4.5
(or to the bromocresol green end point) using a standard solution of HCl
or H2SO4. Results are reported as mg CaCO3/L.
Inorganic Analysis
When the sources of alkalinity are limited to OH–, HCO3-, and CO32-,
separate titrations to a pH of 4.5 (or the bromocresol green end point)
and a pH of 8.3 (or the phenolphthalein end point) allow us to
determine which species are present and their respective
concentrations.
Titration curves for OH–, HCO3-, and CO32- are shown in Figure 6.
For a solution that contains OH– alkalinity only, the volume of strong
acid needed to reach each of the two end points is identical (Figure 6a).
When the only source of alkalinity is CO32-, the volume of strong acid
needed to reach the end point at a pH of 4.5 is exactly twice that
needed to reach the end point at a pH of 8.3 (Figure 6b).
If a solution contains HCO3- alkalinity only, the volume of strong acid needed to
reach the end point at a pH of 8.3 is zero, but that for the pH 4.5 end point is
greater than zero (Figure 6c).
Figure 6 Titration curves for 50.0 mL of (a) 0.10 M NaOH, (b) 0.050 M Na 2CO3,
and (c) 0.10 M NaHCO3 using 0.10 M HCl as a titrant. The dashed lines indicate the
fixed pH end points of 8.3 and 4.5. The color gradients show the phenolphthalein
(red → colorless) and the bromocresol green (blue → green) endpoints. When
titrating to the phenolphthalein endpoint, the titration continues until the last trace
of red is lost.
Organic Analysis
Acid–base titrimetry continues to have a small, but important role for
the analysis of organic compounds in pharmaceutical, biochemical,
agricultural, and environmental laboratories.
Perhaps the most widely employed acid–base titration is the Kjeldahl
analysis for organic nitrogen.
Examples of analytes determined by a Kjeldahl analysis include
caffeine and saccharin in pharmaceutical products, proteins in foods,
and the analysis of nitrogen in fertilizers, sludges, and sediments.
Any nitrogen present in a –3 oxidation state is oxidized quantitatively
to NH4+.
Organic Analysis
Because some aromatic heterocyclic compounds, such as pyridine,

are difficult to oxidize, a catalyst is used to ensure a quantitative
oxidation.
Nitrogen in other oxidation states, such as nitro and azo nitrogens,
are oxidized to N2, which results in a negative determinate error.
Including a reducing agent, such as salicylic acid, converts this
nitrogen to a –3 oxidation state, eliminating this source of error.
Selected Elemental Analyses Based on an Acid–Base
Titration
a The species that is titrated is shown in bold.

Organic Analysis
Several organic functional groups are weak acids or weak bases.
Carboxylic (–COOH), sulfonic (–SO3H) and phenolic (–C6H5OH)
functional groups are weak acids that are titrated successfully in either
aqueous or nonaqueous solvents.
Sodium hydroxide is the titrant of choice for aqueous solutions.
Nonaqueous titrations often are carried out in a basic solvent, such as
ethylenediamine, using tetrabutylammonium hydroxide, (C4H9)4NOH,
as the titrant.
Aliphatic and aromatic amines are weak bases that are titrated using
HCl in aqueous solutions, or HClO4 in glacial acetic acid.
Other functional groups are analyzed indirectly following a reaction
that produces or consumes an acid or base.
Selected Acid–Base Titrimetric Procedures for Organic
Functional Groups Based on the Production or
Consumption of Acid or Base
a The species that is titrated is shown in bold.

b The acetylation reaction [1] is carried out in pyridine to prevent the hydrolysis of
acetic anhydride by water. After the acetylation reaction is complete, water is
added to covert any unreacted acetic anhydride to acetic acid [2].
Organic Analysis
Many pharmaceutical compounds are weak acids or weak bases that

are analyzed by an aqueous or a nonaqueous acid–base titration;
examples include salicylic acid, phenobarbital, caffeine, and
sulfanilamide.
Amino acids and proteins are analyzed in glacial acetic acid using
HClO4 as the titrant.
For example, a procedure for determining the amount of nutritionally
available protein uses an acid–base titration of lysine residues
1. The concept of acid-base in this lesson belongs to which theory:

a. Langmur
b. Lewis
c. Bronsted
d. Faraday
2. According to the theory derived from question 1, acid is defined as a
substance that can......proton
a. Dissociate
b. Donate
c. Accept
d. Capture
3. A base that conjugates with a strong acid has a……strength:
a. Medium
b.Fairly weak
c. Coi như bỏ qua
d. Very weak
4. ……is a solution that is used as a means of keeping pH at a nearly
constant value in a wide variety of chemical applications.
a. Less polar solution
b. Polar solution
c. Buffer solution
d. Dissociated solution
5. Volumetric solution that commonly used to titrate a weak base in a
nonaqueous solvent is:
a. Perchloric acid 0.1 N/hydrochloric acid
b. Perchloric acid 0.1 N/anhydrous acetic acid
c. KOH/CH3OH
d. KOH/CH3CH2OH
6. A sample of 15.0 cm3 HCl is titrated by a volumetric solution of NaOH
0,083 mol.dm-3. The endpoint is obtained with 19.2 cm3. What is the
concentration of HCl?
a. 0.106 mol.dm-3
b. 0.0648 mol.dm-3
c. 0.130 mol.dm-3
d. 0.212 mol.dm-3
7. In an acidic solvent, analytes are……more difficult to dissociate (due to
decrease in proton donation)
a. Ion-exchangers
b. Base
c. Amphoteric ion
d. Acid
PRACTICE EXERCISE
Your company recently received a shipment of salicylic acid, C7H6O3, for

use in the production of acetylsalicylic acid (aspirin). You can accept
the shipment only if the salicylic acid is more than 99% pure. To
evaluate the shipment’s purity, you dissolve a 0.4208-g sample in water
and titrate to the phenolphthalein end point, using 21.92 mL of 0.1354
M NaOH. Report the shipment’s purity as %w/w C7H6O3. Salicylic acid is
a diprotic weak acid with pKa values of 2.97 and 13.74.
PRECIPITATION TITRATIONS
1. Introduction
❑ A reaction in which the analyte and titrant form an insoluble precipitate
also can serve as the basis for a titration.
❑ We call this type of titration a precipitation titration.
❑ Precipitation titration allos us to quantify anions such as Cl -, Br-, CN-,
SCN-, SO42-, CrO42-, PO43-…or cations that form a precipitate with the
mentioned anions.
Introduction
One of the earliest precipitation titrations—developed at the
end of the eighteenth century—was the analysis of K2CO3
and K2SO4 in potash.
Calcium nitrate, Ca(NO3)2, was used as the titrant, which
forms a precipitate of CaCO3 and CaSO4.
The titration’s end point was signaled by noting when the
addition of titrant ceased to generate additional precipitate.
The importance of precipitation titrimetry as an analytical
method reached its zenith in the nineteenth century when
several methods were developed for determining Ag+ and
halide ions.
Introduction
❑ In a precipitation reaction, two or more soluble species combine to form
an insoluble precipitate.
❑ The most common precipitation reaction is a metathesis reaction in
which two soluble ionic compounds exchange parts.
❑ For example, if we add a solution of lead nitrate, Pb(NO3)2, to a
solution of potassium chloride, KCl, a precipitate of lead chloride,
PbCl2, forms.
❑ We usually write a precipitation reaction as a net ionic equation, which
shows only the precipitate and those ions that form the precipitate;
thus, the precipitation reaction for PbCl2 is
Pb2+ (aq) + 2Cl- (aq) ↔ PbCl2 (s)
Introduction
❑ When we write the equilibrium constant for a precipitation reaction,

we focus on the precipitate’s solubility; thus, for PbCl2, the solubility
reaction is
PbCl2 (s) ↔ Pb2+ (aq) + 2Cl- (aq)
and its equilibrium constant, or solubility product, Ksp, is

Ksp = [Pb2 ] [Cl-]2
❑ Even though it does not appear in the Ksp expression, it is important to
remember that the above equation is valid only if PbCl2(s) is present
and in equilibrium with Pb2+ and Cl–.
2. Calculating the Titration Curve
Step 1: Calculate the volume of AgNO3 needed to reach the equivalence
point.
Let’s calculate the titration curve for the titration of 50.0 mL of 0.0500 M
NaCl with 0.100 M AgNO3. The reaction in this case is
Because the reaction’s equilibrium constant is so large
we may assume that Ag+ and Cl– react completely.

The first task is to calculate the volume of Ag+ needed to reach the
equivalence point. The stoichiometry of the reaction requires that
Calculating the Titration Curve
Solving for the volume of Ag+
shows that we need 25.0 mL of Ag+ to reach the equivalence point.

Step 2: Calculate pCl before the equivalence point by determining the
concentration of unreacted NaCl.
Before the equivalence point the titrand, Cl–, is in excess.
The concentration of unreacted Cl– after we add 10.0 mL of Ag+, for
example, is
which corresponds to a pCl (-lg[Cl-]) of 1.60.

Step 3: Calculate pCl at the equivalence point using the Ksp for AgCl to
calculate the concentration of Cl–.
At the titration’s equivalence point, we know that the concentrations of

Ag+ and Cl– are equal.
To calculate the concentration of Cl– we use the Ksp for AgCl; thus
Ksp: the solubility product constant

Solving for x gives [Cl–] as 1.3 × 10–5 M, or a pCl of 4.89.
After the equivalence point, the titrant is in excess.
We first calculate the concentration of excess Ag+ and then use the Ksp
expression to calculate the concentration of Cl–.
For example, after adding 35.0 mL of titrant
Step 4: Calculate pCl after the equivalence point by first calculating the
concentration of excess AgNO3 and then calculating the concentration of Cl–
using the Ksp for AgCl.
After the equivalence point, the titrant is in excess.
We first calculate the concentration of excess Ag+ and then use the Ksp
expression to calculate the concentration of Cl–.
For example, after adding 35.0 mL of titrant
or a pCl of 7.82.
Table 1
Titration of 50.0 mL of 0.0500 M NaCl with 0.100 M AgNO3
Figure 1 Titration curve for the titration of

50.0 mL of 0.0500 M NaCl with 0.100 M
AgNO3. The red points corresponds to the
data in Table 9.18. The blue line shows the
complete titration curve.
3. Selecting and Evaluating the End point
✔ We noted that the first precipitation titration used the cessation of
precipitation to signal the end point.
✔ At best, this is a cumbersome method for detecting a titration’s end
point.
✔ Before precipitation titrimetry became practical, better methods for
identifying the end point were necessary.
Finding the End point With an Indicator
✔ There are three general types of indicators for a precipitation titration,
each of which changes color at or near the titration’s equivalence point.
✔ The first type of indicator is a species that forms a precipitate with the
titrant.
✔ In the Mohr method for Cl– using Ag+ as a titrant, for example, a small
amount of K2CrO4 is added to the titrand’s solution. The titration’s end
point is the formation of a reddish-brown precipitate of Ag2CrO4.
✔ Because CrO42- imparts a yellow color to the solution, which might
obscure the end point, only a small amount of K2CrO4 is added.
MOHR METHOD
Principle
❑ Based on the reaction of Ag+ (from AgNO3) and Cl-
❑ At the end point, K2CrO4 reacts with the excess of Ag+ to form a
reddish-brown precipitate
MOHR METHOD
Application
❑ This direct titration method uses potassium chromate (chromate ions (CrO4
2-
) ) as an indicator in the titration of (Cl- , Br- , and CN-) ions (analyte) with a
silver nitrate standard solution (titrant).
Ksp = 1.8 x 10-10
Ksp = 1.2 x 10-12
❑ AgCl is less soluble than Ag2CrO4 so it will precipitate first

As a result, the end point is always later than the equivalence point.
To compensate for this positive determinate error, an analyte-free
reagent blank is analyzed to determine the volume of titrant needed to
affect a change in the indicator’s color.
Subtracting the end point for the reagent blank from the titrand’s end
point gives the titration’s end point.
Because CrO42- is a weak base, the titrand’s solution is made slightly
alkaline.
If the pH is too acidic, chromate is present as HCrO4- instead of CrO42-,
and the Ag2CrO4 end point is delayed.
The pH also must be less than 10 to avoid the precipitation of silver
hydroxide.
Conditions for Mohr method:
❑ The titrations are performed only in neutral or slightly basic medium to
prevent silver hydroxide and silve formation (at pH > 10).
Ag+ + OH- → AgOH (s)

2AgOH → Ag2O (s) (black precipitate) + H2O
❑ Or the formation of chromic acid at pH < 6.5.
CrO42- + H3O+ → HCrO4- + H2O

2HCrO4- → Cr2O72- (bright orange) + H2O
❑ Reducing [CrO4 2- ] will delay the formation of the precipitate although

more Ag+ to be added to reach end point, which cause error.
✔ A second type of indicator uses a species that forms a colored complex
with the titrant or the titrand.
✔ In the Volhard method for Ag+ using KSCN as the titrant, for example, a
small amount of Fe3+ is added to the titrand’s solution.
✔ The titration’s end point is the formation of the reddish-colored Fe(SCN)2+
complex.
✔ The titration is carried out in an acidic solution to prevent the precipitation
of Fe3+ as Fe(OH)3.
❑ This method uses a back titration with potassium thiocyanate and is
suitable for the determination of (Cl- , Br- , and I-) in acidic solutions.
❑ First, Cl- is precipitated by excess AgNO3
Ag+ (aq) + Cl- (aq) → AgCl (s)

❑ Excess Ag+ is titrated with KSCN in the presence of Fe3+
Ag+ (aq) + SCN- (aq) → AgSCN (s)

❑ When Ag+ has been consumed, a red complex forms as a result of:
Fe3+ (aq) + SCN- (aq) → FeSCN2+ (red complex) (s)

Conditions for Volhard method:
❑ The solution must be acidic, with a concentration of about 1 M in nitric
acid to ensure the complex formed is stable, and to prevent the
precipitation of Iron(III) as Fe(OH)3.
❑ The indicator concentration should not be more than 0.2M (>

0.2 M, [Fe3+ ]: yellow colour)
❑ In case of I-, indicator should not be added until all the I- is
precipitated with Ag+ , since it would be oxidized by the Fe(III).
2Fe3+ + 2I- → 2Fe2+ + I2
❑ The AgX ↓ precipitate must be filtered off, before titrating with SCN to
prevent any error, for example in the case of chloride ion, AgCl will
react with the titrant (SCN-) and cause a diffuse end point.
AgCl + SCN- → AgSCN + Cl-
✔ The third type of end point uses a species that changes color when it
adsorbs to the precipitate.
✔ In the Fajans method for Cl– using Ag+ as a titrant, for example, the
anionic dye dichlorofluoroscein is added to the titrand’s solution.
✔ Before the end point, the precipitate of AgCl has a negative surface
charge due to the adsorption of excess Cl–.
✔ Because dichlorofluoroscein also carries a negative charge, it is
repelled by the precipitate and remains in solution where it has a
greenish-yellow color.
✔ After the end point, the surface of the precipitate carries a positive
surface charge due to the adsorption of excess Ag+.
✔ Dichlorofluoroscein now adsorbs to the precipitate’s surface where its
color is pink. This change in the indicator’s color signals the end point.
Fajans Method
❑ This method uses an adsorption indicator such of Fluorescein
(Dichlorofluorescein) and Eosin.
❑ The indicator adsorb onto the surface of the silver salt precipitate at
the end point.
❑ The adsorption process causes a change in the color of the
indicator.
❑ Common Fajans adsorption indicators are weakly acidic organic
compounds and in alkaline conditions will exist as the conjugate
base,(or Ind-).
❑ This form of the indicator which interacts with the precipitate.
Fajans Method
The mechanism of indicators action:
❑ The best–known adsorption indicator is
fluorescein, which is used to indicate the
equivalence point in the titration of Cl- with Ag+.
Fluorescein is a weak acid, which partially
dissociates in water to form fluoresceinate
anion.
❑ The fluoresceinate anion has a yellow–green

colour in solution.
Fajans Method
❑ When Cl- is titrated with Ag+ in the presence of fluorescein, the
negatively charged fluoresceinate anions are initially repelled by the
negatively charged AgCl colloidal particles, with their primary adsorption
layer of Cl- ions.
❑ Thus the fluorescein remains in a yellow–green colour prior to the
equivalence point.
❑ At the equivalence point, the colloidal AgCl particles undergo an abrupt
change from a negative charge to a positive charge by virtue of Ag+ ions
adsorbed in the primary adsorption layer.
❑ The fluoresceinate ions are strongly adsorbed in the counter–ion layer of
the AgCl colloids, giving these particles a red colour and providing an
end point colour change from yellow–green to red or pink.
Fajans Method
Adsorption indicator whose color when adsorbed to the precipitate is
different from that when it is in solution
4. Quantitative Applications
Although precipitation titrimetry rarely id listed as a standard method of

analysis, it is useful as a secondary analytical method to verify other
analytical methods.
Most precipitation titrations use Ag+ as either the titrand or the titrant. A
titration in which Ag+ is the titrant is called an argentometric titration.
Table 2 provides a list of several typical precipitation titrations.
Table 2
Representative Examples of Precipitation Titrations
a When two reagents are listed, the analysis is by a back titration. The first reagent
is added in excess and the second reagent used to back titrate the excess.
b For those Volhard methods identified with an asterisk (*) the precipitated silver salt
is removed before carrying out the back titration.
Quantitative Calculations
The quantitative relationship between the titrand and the titrant is
determined by the stoichiometry of the titration reaction.
If you are unsure of the balanced reaction, you can deduce the
stoichiometry from the precipitate’s formula.
For example, in forming a precipitate of Ag2CrO4, each mole of
CrO42- reacts with two moles of Ag+.
Example 1
A mixture containing only KCl and NaBr is analyzed by the Mohr
method. A 0.3172-g sample is dissolved in 50 mL of water and
titrated to the Ag2CrO4 end point, requiring 36.85 mL of 0.1120 M
AgNO3. A blank titration requires 0.71 mL of titrant to reach the same
end point. Report the %w/w KCl in the sample.
Solution
To find the moles of titrant reacting with the sample, we first need to correct
for the reagent blank; thus
Titrating with AgNO3 produces a precipitate of AgCl and AgBr. In

forming the precipitates, each mole of KCl consumes one mole of
AgNO3 and each mole of NaBr consumes one mole of AgNO3; thus
We are interested in finding the mass of KCl, so let’s rewrite this equation
in terms of mass. We know that
Solution
which we substitute back into the previous equation
Because this equation has two unknowns—g KCl and g

NaBr—we need another equation that includes both unknowns.
Solution
A simple equation takes advantage of the fact that the sample contains
only KCl and NaBr; thus,
The sample contains 0.262 g of KCl and the %w/w KCl in the sample is
The analysis for I– using the Volhard method requires a back titration. A
typical calculation is shown in the following example.
Example 2
The %w/w I– in a 0.6712-g sample is determined by a Volhard titration.
After adding 50.00 mL of 0.05619 M AgNO3 and allowing the precipitate to
form, the remaining silver is back titrated with 0.05322 M KSCN, requiring
35.14 mL to reach the end point. Report the %w/w I– in the sample.
Solution
There are two precipitates in this analysis: AgNO3 and I– form a
precipitate of AgI, and AgNO3 and KSCN form a precipitate of AgSCN.
Each mole of I– consumes one mole of AgNO3 and each mole of KSCN
consumes one mole of AgNO3; thus
mol AgNO3 = mol I- + mol KSCN
Solving for the moles of I– we find
mol I– = mol AgNO3 – mol KSCN = MAgVAg – MKSCN – VKSCN
mol I– = (0.05619 M) (0.0500 L) – (0.05322 M) (0.05314L)
mol I– = 9.393 x 10-4
The %w/w I– in the sample is

Evaluation of Precipitation Titrimetry
Precipitation titrations also can be extended to the analysis of
mixtures provided there is a significant difference in the solubilities of
the precipitates. Figure 2 shows an example of a titration curve for a
mixture of I– and Cl– using Ag+ as a titrant.
Figure 2 Titration curve for the titration

of a 50.0 mL mixture of 0.0500 M I–
and 0.0500 M Cl– using 0.100 M Ag+
as a titrant. The red arrows show the
end points. Note that the end point for
I– is earlier than the end point for Cl–
because AgI is less soluble than AgCl.
1. In the Mohr method, the titrand’s solution should be
a. Strongly acidic
b. Strongly alkaline
c. Slightly acidic
d. Slightly alkaline
2. Volhard method performed in……solution
a. Strongly acidic
c. Weakly acidic
d. Weakly alkaline
3. Fajans method for quantification of Br-, I- using eosin as indicator in
……solution
a. Strongly acidic
c. Weakly acidic
d. Weakly alkaline
4. Volhard method uses a......titration
a. Direct
b. Displacement
c. Back
d. Indirect
5. Indicator used in Mohr method is:
a. Ammonium alum
b. K2CrO4
c. K2Cr2O7
d. Eosin
Practice Exercise
A 1.963-g sample of an alloy is dissolved in HNO3 and diluted to volume
in a 100-mL volumetric flask. Titrating a 25.00-mL portion with 0.1078 M
KSCN requires 27.19 mL to reach the end point. Calculate the %w/w Ag
in the alloy.
REDOX TITRATIONS
1. INTRODUCTION
❑ The earliest Redox titration took advantage of chlorine’s oxidizing power.
❑ In 1787, Claude Berthollet introduced a method for the quantitative
analysis of chlorine water (a mixture of Cl2, HCl, and HOCl) based on its
ability to oxidize indigo, a dye that is colorless in its oxidized state.
❑ In 1814, Joseph Gay-Lussac developed a similar method to determine
chlorine in bleaching powder. In both methods the end point is a change
in color.
❑ Before the equivalence point the solution is colorless due to the
oxidation of indigo. After the equivalence point, however, unreacted
indigo imparts a permanent color to the solution.
INTRODUCTION
❑ The number of redox titrimetric methods increased in the mid-1800s with
the introduction of MnO4-, Cr2O72-, and I2 as oxidizing titrants, and of Fe2+
and S2O32- as reducing titrants.
❑ Even with the availability of these new titrants, redox titrimetry was slow
to develop due to the lack of suitable indicators. A titrant can serve as its
own indicator if its oxidized and its reduced forms differ significantly in
color.
❑ For example, the intensely purple MnO4- ion serves as its own indicator
since its reduced form, Mn2+, is almost colorless.
❑ Other titrants require a separate indicator. The first such indicator,
diphenylamine, was introduced in the 1920s.
❑ Other redox indicators soon followed, increasing the applicability of
redox titrimetry.
What is a redox reaction
❑ Redox reaction is any chemical reaction in which the oxidation states of
atoms are changed
❑ Characterized by the transfer of electron between chemical species
✔ Oxidation: the loss of e- (reducing agent)
✔ Reduction: the gain of e- (oxidizing agent)
✔ Upon the oxidation to occur, there is a reduction.
Example: adding ferrous (III) chloride solution in tin (II) chloride
solution
2FeCl3 + SnCl2 2FeCl2 + SnCl4
2Fe3++ 2e 2Fe2+
Sn2+ - 2e Sn4+
2Fe3++ Sn2+ 2Fe2++ Sn4+
❑ Reducing agent and oxidizing agent
✔ Case 1: 1 chemical and 1 electrode (electrochemical reaction)
Platinum electrode Platinum electrode
Depending on electrode potency, electrode donates electron or accepts it

✔ Case 2: 2 chemicals (chemical reaction)
Titrant
Titrand
Remark
❑ Reaction rate
✔ Slow: increase temperature, adding catalyst
✔ Multi-step reaction
✔ Electron transition is a link in the chain (breaking bond,
protonation, rearrangement of molecule)
Redox potential
❑ Redox potential is a measure of the tendency of a chemical species to
acquire electrons from or lose electrons to an electrode and thereby be
reduced or oxidised respectively.
❑ Redox potential is measured in volts (V), or millivolts (mV).
❑ Each species has its own intrinsic redox potential; for example, the more
positive the reduction potential (reduction potential is more often used
due to general formalism in electrochemistry), the greater the species'
affinity for electrons and tendency to be reduced.
❑ Galvanic cell (voltaic cell) is a simple device with which chemical
energy is converted into electrical energy.
❑ Galvanic cells consist of two separate compartments called half
cells containing electrolyte solutions and electrodes that can be
connected in a circuit.
❑ Two dissimilar metals (e.g., copper and zinc) are immersed in an
electrolyte.
❑ If the metals are connected by an external circuit, one metal is
reduced (i.e., gains electrons) while the other metal is oxidized (i.e.,
loses electrons).
A redox reaction with two half cells

❑ The standard hydrogen electrode (SHE) is the reference from which all
standard redox potentials are determined, and has been assigned an
arbitrary half cell potential of 0.0 mV.
❑ However, it is fragile and impractical for routine laboratory use.
Therefore, other more stable reference electrodes such as silver
chloride and saturated calomel (SCE) are commonly used because of
their more reliable performance.
Redox potential
❑ Because a redox reaction involves a transfer of electrons from a reducing
agent to an oxidizing agent, it is convenient to consider the reaction’s
thermodynamics in terms of the electron.
❑ For a reaction in which one mole of a reactant undergoes oxidation or
reduction, the net transfer of charge, Q, in coulombs is Q = nF where n is
the moles of electrons per mole of reactant, and F is Faraday’s constant
(96 485 C/mol). The free energy, ΔG, to move this charge, Q, over a
change in potential, E, is ΔG = EQ
❑ The change in free energy (in kJ/mole) for a redox reaction, therefore, is
ΔG = -nFE where ΔG has units of kJ/mol. The minus sign in equation is
the result of a different convention for assigning a reaction’s favorable
direction.
Redox potential
❑ In thermodynamics, a reaction is favored when ΔG is negative, but an
oxidation-reduction reaction is favored when E is positive.
❑ The Nernst equation
T = 5 oC (298 oK)
lnQ = 2.303 logQ
where Eo is the potential under standard-state

conditions.
Walther Nernst
F is Faraday’s constant (96 485 C/mol).
(1864 – 1941)
n is the moles of electrons per mole of reactant
R: universal gas constant (8.314 J. K-1.mol-1
T: temperature (in kelvins)
Redox potential
❑ A redox reaction’s standard potential, Eo, provides an alternative way of
expressing its equilibrium constant and, therefore, its equilibrium
position.
❑ Because a reaction at equilibrium has a ΔG of zero, the potential, E,
also is zero at equilibrium. Substituting these values into equation
and rearranging provides a relationship between Eo and K.

Redox potential
❑ We generally do not tabulate standard potentials for redox reactions.
❑ Instead, we calculate Eo using the standard potentials for the
corresponding oxidation half-reaction and reduction half-reaction.
❑ By convention, standard potentials are provided for reduction
half-reactions. The standard potential for a redox reaction, Eo, is
Eo = Eredo - Eoxo
where Ered o and Eox o are the standard reduction potentials for the
reduction half-reaction and the oxidation half-reaction.
❑ Because we cannot measure the potential for a single half-reaction, we
arbitrarily assign a standard reduction potential of zero to a reference
half-reaction
Example
Calculate (a) the standard potential, (b) the equilibrium constant, and (c)
the potential when [Ag+] = 0.020 M and [Cd2+] = 0.050 M, for the
following reaction at 25 oC.
Solution
(a) In this reaction Cd is oxidized and Ag+ is reduced. The standard cell
potential, therefore, is
Example
Solution
(b) To calculate the equilibrium constant we substitute appropriate
values into equation
Example
Solution
Solving for K gives the equilibrium constant as
logK = 40.6558
K = 4.527 x 1040
Example
Solution
(c) To calculate the potential when [Ag+] is 0.020 M and [Cd2+] is 0.050 M,
we use the appropriate relationship for the reaction quotient, Q, in equation
Standard Reduction Potentials for selected reduction reactions
Conditions for formal potentials (Eo´) are listed next to the potential.
Standard Reduction Potentials for selected reduction reactions
Conditions for formal potentials (Eo´) are listed next to the potential.
Redox Titration Curves
❑ For a redox titration it is convenient to monitor the titration reaction’s
potential instead of the concentration of one species.
❑ Nernst equation relates a solution’s potential to the concentrations of
reactants and products that participate in the redox reaction.
❑ Consider, for example, a titration in which a titrand in a reduced state,
Ared, reacts with a titrant in an oxidized state, Box.
Ared + Box ↔ Aox + Bred
where Aox is the titrand’s oxidized form, Bred is the titrant’s reduced form,
and the stoichiometry between the two is 1:1. The reaction’s potential,
Erxn, is the difference between the reduction potentials for each
half-reaction.
❑ After each addition of titrant the reaction between the titrand and the
titrant reaches a state of equilibrium.
❑ Because the potential at equilibrium is zero, the titrand’s and the
titrant’s reduction potentials are identical.
❑ This is an important observation as it allows us to use either

half-reaction to monitor the titration’s progress.
❑ Before the equivalence point the titration mixture consists of
appreciable quantities of the titrand’s oxidized and reduced forms.
❑ The concentration of unreacted titrant, however, is very small.
❑ The potential, therefore, is easier to calculate if we use the Nernst
equation for the titrand’s half-reaction
❑ After the equivalence point it is easier to calculate the potential using
the Nernst equation for the titrant’s half-reaction.

Let’s calculate the titration curve for the titration of 50.0 mL of 0.100 M Fe2+
with 0.100 M Ce4+ in a matrix of 1 M HClO4. The reaction in this case is
In 1 M HClO4, the formal potential for the reduction of Fe3+ to Fe2+ is

+0.767 V, and the formal potential for the reduction of Ce4+ to Ce3+ is
+1.70 V.
❑ Because the equilibrium constant for reaction is very large (approximately
6 × 1015), we may assume that the analyte and titrant react completely.
❑ Step 1: is to calculate the volume of Ce4+ needed to reach the titration’s
equivalence point. From the reaction’s stoichiometry we know that
❑ Solving for the volume of Ce4+ gives the equivalence point volume as
❑ Step 2: Calculate the potential before the equivalence point by
determining the concentrations of the titrand’s oxidized and reduced
forms, and using the Nernst equation for the titrand’s reduction
half-reaction.
❑ Before the equivalence point, the concentration of unreacted Fe2+ and
the concentration of Fe3+ are easy to calculate.
❑ For this reason we find the potential using the Nernst equation for the
Fe3+/Fe2+ half-reaction
❑ For example, the concentrations of Fe2+ and Fe3+ after adding 10.0 mL of
titrant are
Substituting these concentrations into equation

gives the potential as
Step 3: Calculate the potential after the equivalence point by determining the
concentrations of the titrant’s oxidized and reduced forms, and using the
Nernst equation for the titrant’s reduction half-reaction.
❑ After the equivalence point, the concentration of Ce3+ and the

concentration of excess Ce4+ are easy to calculate.
❑ For this reason we find the potential using the Nernst equation for the
Ce4+/Ce3+ half-reaction in a manner similar to that used above to
calculate potentials before the equivalence point.
Table 1
Data for the Titration of 50.0 mL of 0.100 M Fe2+ with
0.100 M Ce4+
❑ For example, after adding 60.0 mL of titrant, the concentrations of Ce3+
and Ce4+ are
❑ Substituting these concentrations into

gives a potential of
Step 4: Calculate the potential at the equivalence point.
❑ At the titration’s equivalence point, the potential, Eeq, in equation
and
are identical. Adding the equations together to gives
❑ Because [Fe2+ ] = [Ce4+] and [Ce3+] = [Fe3+] at the equivalence point, the
log term has a value of zero and the equivalence point’s potential is
Figure 1 Titration curve for the titration of 50.0 mL of 0.100 M Fe2+
with 0.100 M Ce4+. The red points correspond to the data in Table 1.
The blue line shows the complete titration curve.
❑ A redox titration’s equivalence point occurs when we react
stoichiometrically equivalent amounts of titrand and titrant.
❑ As is the case for acid–base titrations and complexation titrations, we
estimate the equivalence point of a redox titration using an experimental
end point.
❑ A variety of methods are available for locating a redox titration’s end point,
including indicators and sensors that respond to a change in the solution
conditions.
❑ If the stoichiometry of a redox titration is 1:1—that is, one mole of titrant
reacts with each mole of titrand—then the equivalence point is symmetric.
❑ If the titration reaction’s stoichiometry is not 1:1, then the equivalence
point is closer to the top or to the bottom of the titration curve’s sharp rise.
In this case we have an asymmetric equivalence point.
Finding the End point with an Indicator
❑ Three types of indicators are used to signal a redox titration’s end point.
❑ The oxidized and reduced forms of some titrants, such as MnO4-, have
different colors.
❑ A solution of MnO4- is intensely purple. In an acidic solution, however,
permanganate’s reduced form, Mn2+, is nearly colorless.
❑ When using MnO4- as a titrant, the titrand’s solution remains colorless
until the equivalence point. The first drop of excess MnO4- produces a
permanent tinge of purple, signaling the end point.
❑ Some indicators form a colored compound with a specific oxidized or
reduced form of the titrant or the titrand.
❑ Starch, for example, forms a dark purple complex with I3-. We can use
this distinct color to signal the presence of excess I3- as a titrant, a
change in color from colorless to purple or the completion of a reaction
that consumes I3- as the titrand—a change in color from purple to
colorless.
❑ Another example of a specific indicator is thiocyanate, SCN–, which
forms the soluble red-colored complex of Fe(SCN)2+ in the presence of
Fe3+.
❑ The most important class of indicators are substances that do not
participate in the redox titration, but whose oxidized and reduced
forms differ in color.
❑ When we add a redox indicator to the titrand, the indicator imparts a
color that depends on the solution’s potential.
❑ As the solution’s potential changes with the addition of titrant, the
indicator eventually changes oxidation state and changes color,
signaling the end point.
To understand the relationship between potential and an indicator’s
color, consider its reduction half-reaction
Inox + ne- ↔ Inred
where Inox and Inred are, respectively, the indicator’s oxidized and reduced
forms.
The Nernst equation for this half-reaction is
As shown in Figure 2, if we assume the indicator’s color changes from that

of Inox to that of Inred when the ratio [Inred]/[Inox] changes from 0.1 to 10,
then the end point occurs when the solution’s potential is within the range
Figure 2 Diagram showing the relationship

between E and an indicator’s color. The ladder
diagram defines potentials where Inred and
Inox are the predominate species.
Table 2
Selected Examples of Redox Indicators
Examples of an appropriate and an inappropriate indicator for the titration of
Fe2+ with Ce4+
Figure 3 Titration curve for titration of 50.0 mL of 0.100 M Fe2+ with 0.100 M
Ce4+. The end point transitions for the indicators diphenylamine sulfonic acid
and ferroin are superimposed on the titration curve. Because the transition
for ferroin is too small to see on the scale of the x-axis—it requires only 1–2
drops of titrant—the color change is expanded to the right.
Adjusting the Titrand’s Oxidation State
❑ If a redox titration is to be used in a quantitative analysis, the titrand

initially must be present in a single oxidation state.
❑ For example, iron is determined by a redox titration in which Ce4+ oxidizes
Fe2+ to Fe3+.
❑ Depending on the sample and the method of sample preparation, iron
initially may be present in both the +2 and +3 oxidation states. Before
titrating, we must reduce any Fe3+ to Fe2+ if we want to determine the total
concentration of iron in the sample.
❑ This type of pretreatment is accomplished using an auxiliary reducing
agent or oxidizing agent.
Quantitative Applications
❑ A metal that is easy to oxidize—such as Zn, Al, and Ag—can serve as
an auxiliary reducing agent.
❑ The metal, as a coiled wire or powder, is added to the sample where it
reduces the titrand.
❑ Because any unreacted auxiliary reducing agent will react with the
titrant, it is removed before we begin the titration by removing the
coiled wire or by filtering.
❑ An alternative method for using an auxiliary reducing agent is to
immobilize it in a column.
❑ To prepare a reduction column an aqueous slurry of the finally divided
metal is packed in a glass tube equipped with a porous plug at the
bottom.
❑ The sample is placed at the top of the column and moves through the
column under the influence of gravity or vacuum suction.
❑ The length of the reduction column and the flow rate are selected to
ensure the analyte’s complete reduction.
❑ Two common reduction columns are used. In the Jones reductor the
column is filled with amalgamated zinc, Zn(Hg), which is prepared by
briefly placing Zn granules in a solution of HgCl2.
❑ Oxidation of zinc provides the electrons for reducing the titrand
❑ In the Walden reductor the column is filled with granular Ag metal.

❑ The solution containing the titrand is acidified with HCl and passed
through the column where the oxidation of silver provides the
necessary electrons for reducing the titrand.
Table 3
Examples of Reactions For Reducing a Titrand’s
Oxidation State Using a Reduction Column
❑ Several reagents are used as auxiliary oxidizing agents, including
ammonium peroxydisulfate, (NH4)2S2O8, and hydrogen peroxide, H2O2.
Peroxydisulfate is a powerful oxidizing agent that is capable of oxidizing
Mn2+ to MnO4-, Cr3+ to Cr2O72-, and Ce3+ to Ce4+.
❑ Excess peroxydisulfate is destroyed by briefly boiling the solution. The

reduction of hydrogen peroxide in an acidic solution provides another
method for oxidizing a titrand
❑ Excess H2O2 is destroyed by briefly boiling the solution.

❑ If it is to be used quantitatively, the titrant’s concentration must remain
stable during the analysis.
❑ Because a titrant in a reduced state is susceptible to air oxidation,
most redox titrations use an oxidizing agent as the titrant. There are
several common oxidizing titrants, including MnO4-, Ce4+, Cr2O72-, and
I3-.
❑ Which titrant is used often depends on how easily it oxidizes the
titrand.
❑ A titrand that is a weak reducing agent needs a strong oxidizing titrant
if the titration reaction is to have a suitable end point.
❑ The two strongest oxidizing titrants are MnO4- and Ce4+, for which the
reduction half-reactions are
solution of Ce4+ in 1 M H2SO4 usually is prepared from the primary

standard cerium ammonium nitrate, Ce(NO3)4•2NH4NO3.
❑ When prepared using a reagent grade material, such as Ce(OH)4,
the solution is standardized against a primary standard reducing
agent such as Na2C2O4 or Fe2+ (prepared from iron wire) using
ferroin as an indicator. Despite its availability as a primary standard
and its ease of preparation, Ce4+ is not used as frequently as
MnO4- because it is more expensive.
❑ Despite its availability as a primary standard and its ease of
preparation, Ce4+ is not used as frequently as MnO4- because it is
more expensive
The standardization reactions are:
❑ A solution of MnO4- is prepared from KMnO4, which is not available as a
primary standard.
❑ An aqueous solution of permanganate is thermodynamically unstable due
to its ability to oxidize water.
❑ This reaction is catalyzed by the presence of MnO2, Mn2+, heat, light, and
the presence of acids and bases.
❑ A moderately stable solution of permanganate is prepared by boiling it for
an hour and filtering through a sintered glass filter to remove any solid
MnO2 that precipitates.
❑ Standardization is accomplished against a primary standard reducing
agent such as Na2C2O4 or Fe2+ (prepared from iron wire), with the pink
color of excess MnO4- signaling the end point.
❑ A solution of MnO4- prepared in this fashion is stable for 1–2 weeks,

although you should recheck the standardization periodically.
The standardization reactions are:

❑ Potassium dichromate is a relatively strong oxidizing agent whose
principal advantages are its availability as a primary standard and its
long term stability when in solution.
❑ It is not, however, as strong an oxidizing agent as MnO4- or Ce4+,
which makes it less useful when the titrand is a weak reducing agent.
Its reduction half-reaction is
❑ Although a solution of Cr2O72- is orange and a solution of Cr3+ is green,

neither color is intense enough to serve as a useful indicator.
❑ Diphenylamine sulfonic acid, whose oxidized form is red-violet and
reduced form is colorless, gives a very distinct end point signal with
Cr2O72-.
❑ Iodine is another important oxidizing titrant. Because it is a weaker
oxidizing agent than MnO4-, Ce4+, and Cr2O72-, it is useful only when the
titrand is a stronger reducing agent.
❑ This apparent limitation, however, makes I2 a more selective titrant for the
analysis of a strong reducing agent in the presence of a weaker reducing
agent. The reduction half-reaction for I2 is
I2(aq) + 2e- ↔ 2I-(aq)
❑ Because iodine is not very soluble in water, solutions are prepared by
adding an excess of I–. The complexation reaction
I2(aq) + I-(aq) ↔ I3-(aq)
❑ increases the solubility of I2 by forming the more soluble triiodide ion, I3-.
Even though iodine is present as I3- instead of I2, the number of electrons
in the reduction half-reaction is unaffected. I3-(aq) + 2e- ↔ 3I-(aq)
❑ Solutions of I3- normally are standardized against Na2S2O3 using starch

as a specific indicator for I3-.
❑ An oxidizing titrant such as MnO4-, Ce4+, Cr2O72-, and I3-, is used when
the titrand is in a reduced state.
❑ If the titrand is in an oxidized state, we can first reduce it with an
auxiliary reducing agent and then complete the titration using an
oxidizing titrant. Alternatively, we can titrate it using a reducing titrant.
❑ Iodide is a relatively strong reducing agent that could serve as a
reducing titrant except that its solutions are susceptible to the
air-oxidation of I– to I3-.
3I- (aq) ↔ I3- (aq) + 2e-
❑ Instead, adding an excess of KI reduces the titrand and releases a
stoichiometric amount of I3-.
❑ The amount of I3- produced is then determined by a back titration
using thiosulfate, S2O32-, as a reducing titrant.
2S2O32- (aq) ↔ S4O62- (aq) + 2e-
❑ Solutions of S2O32- are prepared using Na2S2O3•5H2O and are
standardized before use.
❑ Standardization is accomplished by dissolving a carefully weighed
portion of the primary standard KIO3 in an acidic solution that contains
an excess of KI. The reaction between IO3- and I–
IO3- + 8I-(aq) + 6H+ (aq) ↔ 3I3- + 3H2O (l)
liberates a stoichiometric amount of I3-.

❑ By titrating this I3- with thiosulfate, using starch as a visual indicator, we
can determine the concentration of S2O32- in the titrant.
❑ Although thiosulfate is one of the few reducing titrants that is not readily
oxidized by contact with air, it is subject to a slow decomposition to
bisulfite and elemental sulfur.
❑ If used over a period of several weeks, a solution of thiosulfate is
restandardized periodically.
❑ Several forms of bacteria are able to metabolize thiosulfate, which leads
to a change in its concentration. This problem is minimized by adding a
preservative such as HgI2 to the solution.
❑ Another useful reducing titrant is ferrous ammonium sulfate,
Fe(NH4)2(SO4)2•6H2O, in which iron is present in the +2 oxidation state.
❑ A solution of Fe2+ is susceptible to air-oxidation, but when prepared in 0.5
M H2SO4 it remains stable for as long as a month.
❑ Periodic restandardization with K2Cr2O7 is advisable. Ferrous ammonium
sulfate is used as the titrant in a direct analysis of the titrand, or, it is
added to the titrand in excess and the amount of Fe3+ produced
determined by back titrating with a standard solution of Ce4+ or Cr2O72-
Inorganic Analysis
Representative Method
Determination of Total Chlorine Residual
Description of the Method
The chlorination of a public water supply produces several
chlorine-containing species, the combined concentration of which is called
the total chlorine residual. Chlorine is present in a variety of chemical
states, including the free residual chlorine, which consists of Cl2, HOCl and
OCl–, and the combined chlorine residual, which consists of NH2Cl, NHCl2,
and NCl3. The total chlorine residual is determined by using the oxidizing
power of chlorine to convert I– to I3-. The amount of I3- formed is then
determined by titrating with Na2S2O3 using starch as an indicator.
Regardless of its form, the total chlorine residual is reported as if Cl2 is the
only source of chlorine, and is reported as mg Cl/L.
Inorganic Analysis
❑ The efficiency of chlorination depends on the form of the chlorinating
species.
❑ There are two contributions to the total chlorine residual—the free
chlorine residual and the combined chlorine residual.
❑ The free chlorine residual includes forms of chlorine that are available
for disinfecting the water supply. Examples of species that contribute to
the free chlorine residual include Cl2, HOCl and OCl–.
❑ The combined chlorine residual includes those species in which chlorine
is in its reduced form and, therefore, no longer capable of providing
disinfection.
❑ Species that contribute to the combined chlorine residual are NH2Cl,
NHCl2 and NCl3.
Inorganic Analysis
❑ When a sample of iodide-free chlorinated water is mixed with an excess
of the indicator N,N-diethyl-p-phenylenediamine (DPD), the free chlorine
oxidizes a stoichiometric portion of DPD to its red-colored form.
❑ The oxidized DPD is then back-titrated to its colorless form using ferrous
ammonium sulfate as the titrant. The volume of titrant is proportional to
the free residual chlorine.
❑ Having determined the free chlorine residual in the water sample, a small
amount of KI is added, which catalyzes the reduction of monochloramine,
NH2Cl, and oxidizes a portion of the DPD back to its red-colored form.
❑ Titrating the oxidized DPD with ferrous ammonium sulfate yields the
amount of NH2Cl in the sample. The amount of dichloramine and
trichloramine are determined in a similar fashion.
Inorganic Analysis
❑ The methods described above for determining the total, free, or
combined chlorine residual also are used to establish a water supply’s
chlorine demand.
❑ Chlorine demand is defined as the quantity of chlorine needed to react
completely with any substance that can be oxidized by chlorine, while
also maintaining the desired chlorine residual.
❑ It is determined by adding progressively greater amounts of chlorine to
a set of samples drawn from the water supply and determining the total,
free, or combined chlorine residual.
Inorganic Analysis
❑ Another important example of redox titrimetry, which finds applications in
both public health and environmental analysis, is the determination of
dissolved oxygen.
❑ In natural waters, such as lakes and rivers, the level of dissolved O2 is
important for two reasons: it is the most readily available oxidant for the
biological oxidation of inorganic and organic pollutants; and it is
necessary for the support of aquatic life.
❑ In a wastewater treatment plant dissolved O2 is essential for the aerobic
oxidation of waste materials. If the concentration of dissolved O2 falls
below a critical value, aerobic bacteria are replaced by anaerobic
bacteria, and the oxidation of organic waste produces undesirable
gases, such as CH4 and H2S.
Inorganic Analysis
❑ One standard method for determining dissolved O2 in natural waters and
wastewaters is the Winkler method.
❑ A sample of water is collected without exposing it to the atmosphere,
which might change the concentration of dissolved O2.
❑ The sample first is treated with a solution of MnSO4 and then with a
solution of NaOH and KI. Under these alkaline conditions the dissolved
oxygen oxidizes Mn2+ to MnO2.
❑ After the reaction is complete, the solution is acidified with H2SO4.

Under the now acidic conditions, I– is oxidized to I3- by MnO2.
Inorganic Analysis
❑ The amount of I3- that forms is determined by titrating with S2O32- using
starch as an indicator.
❑ The Winkler method is subject to a variety of interferences and several
modifications to the original procedure have been proposed.
❑ For example, NO2- interferes because it reduces I3- to I– under acidic
conditions.
❑ This interference is eliminated by adding sodium azide, NaN3, which
reduces NO2- to N2. Other reducing agents, such as Fe2+, are
eliminated by pretreating the sample with KMnO4 and destroying any
excess permanganate with K2C2O4.
Inorganic Analysis
❑ Another important example of redox titrimetry is the determination of
water in nonaqueous solvents.
❑ The titrant for this analysis is known as the Karl Fischer reagent and
consists of a mixture of iodine, sulfur dioxide, pyridine, and methanol.
❑ Because the concentration of pyridine is sufficiently large, I2 and SO2
react with pyridine (py) to form the complexes py•I2 and py•SO2.
❑ When added to a sample that contains water, I2 is reduced to I– and
SO2 is oxidized to SO3.
❑ Methanol is included to prevent the further reaction of py•SO3 with water.

The titration’s end point is signaled when the solution changes from the
product’s yellow color to the brown color of the Karl Fischer reagent.
Organic Analysis
❑ Redox titrimetry also is used for the analysis of organic analytes.
❑ One important example is the determination of the chemical oxygen
demand (COD) of natural waters and wastewaters.
❑ The COD is a measure of the quantity of oxygen necessary to oxidize
completely all the organic matter in a sample to CO2 and H2O.
❑ Because no attempt is made to correct for organic matter that is
decomposed biologically, or for slow decomposition kinetics, the COD
always overestimates a sample’s true oxygen demand.
❑ The determination of COD is particularly important in the management
of industrial wastewater treatment facilities where it is used to monitor
the release of organic-rich wastes into municipal sewer systems or into
the environment.
Organic Analysis
❑ A sample’s COD is determined by refluxing it in the presence of excess
K2Cr2O7, which serves as the oxidizing agent.
❑ The solution is acidified with H2SO4, using Ag2SO4 to catalyze the
oxidation of low molecular weight fatty acids. Mercuric sulfate, HgSO4, is
added to complex any chloride that is present, which prevents the
precipitation of the Ag+ catalyst as AgCl.
Organic Analysis
❑ Under these conditions, the efficiency for oxidizing organic matter is
95–100%. After refluxing for two hours, the solution is cooled to room
temperature and the excess Cr2O72- determined by a back titration using
ferrous ammonium sulfate as the titrant and ferroin as the indicator.
❑ Because it is difficult to remove completely all traces of organic matter
from the reagents, a blank titration is performed.
❑ The difference in the amount of ferrous ammonium sulfate needed to
titrate the sample and the blank is proportional to the COD.
Organic Analysis
❑ Iodine has been used as an oxidizing titrant for a number of compounds
of pharmaceutical interest.
❑ Earlier we noted that the reaction of S2O32- with I3- produces the
tetrathionate ion, S4O62-. The tetrathionate ion is actually a dimer that
consists of two thiosulfate ions connected through a disulfide (–S–S–)
linkage.
❑ In the same fashion, I3- is used to titrate mercaptans of the general
formula RSH, forming the dimer RSSR as a product. The amino acid
cysteine also can be titrated with I3-.
❑ The product of this titration is cystine, which is a dimer of cysteine.
Triiodide also is used for the analysis of ascorbic acid (vitamin C) by
oxidizing the enediol functional group to an alpha diketone
Organic Analysis
+ 2H+ + 2e-
and for the analysis of reducing sugars, such as glucose, by oxidizing the
aldehyde functional group to a carboxylate ion in a basic solution.
❑ An organic compound that contains a hydroxyl, a carbonyl, or an

amine functional group adjacent to an hydoxyl or a carbonyl group
can be oxidized using metaperiodate, IO4-, as an oxidizing titrant.
Organic Analysis
❑ A two-electron oxidation cleaves the C–C bond between the two
functional groups with hydroxyl groups oxidized to aldehydes or ketones,
carbonyl groups oxidized to carboxylic acids, and amines oxidized to an
aldehyde and an amine (ammonia if a primary amine).
❑ The analysis is conducted by adding a known excess of IO4- to the
solution that contains the analyte and allowing the oxidation to take
place for approximately one hour at room temperature.
❑ When the oxidation is complete, an excess of KI is added, which
converts any unreacted IO4- to IO3- and I3-.
❑ The I3- is then determined by titrating with S2O32- using starch as an

indicator.
Example
The amount of ascorbic acid, C6H8O6, in orange juice is
determined by oxidizing ascorbic acid to dehydroascorbic
acid, C6H6O6, with a known amount of I3-, and back
titrating the excess I3- with Na2S2O3. A 5.00-mL sample of
filtered orange juice is treated with 50.00 mL of 0.01023 M
I3-. After the oxidation is complete, 13.82 mL of 0.07203 M
Na2S2O3 is needed to reach the starch indicator end point.
Report the concentration ascorbic acid in mg/100 mL.
Solution
❑ For a back titration we need to determine the stoichiometry
between I3- and the analyte, C6H8O6,
❑ and between I3- and the titrant, Na2S2O3.
❑ in the titration reaction, I3- is reduced to I– and S2O32- is oxidized to
S4O62-. Reducing I3- to 3I– requires two elections as each iodine
changes from an oxidation state of –⅓ to –1. In oxidizing S2O32- to
S4O62-, each sulfur changes its oxidation state from +2 to +2.5,
releasing one electron for each S2O32-. A conservation of
electrons, therefore, requires that each mole of I3- reacts with two
moles of S2O32-.
Solution
❑ In oxidizing ascorbic acid to dehydroascorbic acid, the oxidation state
of carbon changes from +⅔ in C6H8O6 to +1 in C6H6O6.
❑ Each carbon releases ⅓ of an electron, or a total of two electrons per
ascorbic acid. As we learned, reducing I3- requires two electrons; thus,
a conservation of electrons requires that each mole of ascorbic acid
consumes one mole of I3-.
The total moles of I3- that react with C6H8O6 and with Na2S2O3 is
(0.01023 M) (0.05000 L) = 5.115 x 10-4 mol I3-
The back titration consumes
Solution
Subtracting the moles of I3- that react with Na2S2O3 from the total moles
of I3- gives the moles reacting with ascorbic acid.
The grams of ascorbic acid in the 5.00-mL sample of orange juice is
There are 2.43 mg of ascorbic acid in the 5.00-mL sample, or 48.6 mg

per 100 mL of orange juice.
1. Redox reaction is any reaction corresponding to the exchange of

electrons between the two chemical species: one donates electrons
called ……(A)……whereas the other accepts electrons called ……(B)……
a. (A) = reducing agent (B) = oxidizing agent.
b. (A) = acid (B) = base.
c. (A) = conjugate acid (B) = conjugate base
d. (A) = oxidizing agent (B) = reducing agent
2. Reducer and oxidizer are ……(A)……[chemical reaction] or a(n
)……(B)……and a(n)……(C)……with an appropriate potential
[electrochemical reaction]
a. (A) = neutral agents; (B) = acid; (C): base.
b. (A) = chemical species; (B) = oxidizer; (C): reducer.
c. (A) = chemical species; (B) = chemical specie; (C): electrode.
d. (A) = amphoteric agents; (B) = chemical species; (C): electrode.
3. Redox reaction is any reaction in which an exchange of …from this
reactant to other reactant
a. Proton.
b. Electron
c. Cation
d. Ion
4. Redox reaction is a process of donation-acceptance …(A)…that often
occurs …(B)…in demand an increase of temperature as well as adding
of catalyst .
a. (A) = neutral agents (B) = rapidly.
b. (A) = protons (B) = slowly.
c. (A) = electrons (B) = slowly.
d. (A) = protons (B) = rapidly.
5. The standard hydrogen electrode (SHE) is the reference from which all
standard redox potentials are determined, and has been assigned an
arbitrary half cell potential of ……mV.
a. 0.00.
b. 1.00
c. ±1.00
d. ±10.0
6. A …….., Eo, provides an alternative way of expressing its equilibrium

constant and, therefore, its equilibrium position
a. Redox reaction’s apparent potential
b. Redox reaction’s equilibrium potential
c. Redox reaction’s standard potential
d. Equivalence point
7. A metal can generate relevant ions of various valency. Ion with highest
positive charge is in …(A)…. Ion with lowest positive charge is in
…(A)…. Ion có điện tích dương lớn nhất tương ứng với dạng…(B)…
a. (A) = reduced form (B) = oxidized form.
b. (A) = oxidized form (B) = reduced form.
c. (A) = acid (B) = base.
d. (A) = base (B) = acid.
8. The Karl Fischer reagent consists of a mixture of:
a. iodine, carbon dioxide, pyridine, and methanol
b. iodine, sulfur dioxide, and methanol
c. iodine, sulfur dioxide, pyridine, and methanol
d. iodine, sulfur dioxide, pyridine
Practice Exercise 1
For the following reaction at 25 oC
calculate (a) the standard potential, (b) the equilibrium constant, and
(c) the potential under these conditions: [Fe2+] = 0.50 M, [Fe3+] = 0.10
M, [MnO4- ] = 0.025 M, [Mn2+] = 0.015 M, and a pH of 7.00.
Practice Exercise 2
The purity of a sample of sodium oxalate, Na2C2O4, is determined by

titrating with a standard solution of KMnO4. If a 0.5116-g sample
requires 35.62 mL of 0.0400 M KMnO4 to reach the titration’s end point,
what is the %w/w Na2C2O4 in the sample.
COMPLEXATION TITRATIONS
1. Introduction
The earliest examples of metal–ligand complexation titrations are
Liebig’s determinations, in the 1850s, of cyanide and chloride using,
respectively, Ag+ and Hg2+ as the titrant.
Practical analytical applications of complexation titrimetry were slow to
develop because many metals and ligands form a series of
metal–ligand complexes.
Liebig’s titration of CN– with Ag+ was successful because they form a
single, stable complex of Ag(CN)2-, which results in a single, easily
identified end point.
Other metal–ligand complexes, such as CdI42-, are not analytically
useful because they form a series of metal–ligand complexes (CdI+,
CdI2(aq), CdI3- and CdI42-) that produce a sequence of poorly defined
end points.
1. Introduction
In 1945, Schwarzenbach introduced aminocarboxylic acids as
multidentate ligands. The most widely used of these new
ligands—ethylenediaminetetraacetic acid, or EDTA—forms a strong
1:1 complex with many metal ions.
The availability of a ligand that gives a single, easily identified end
point made complexation titrimetry a practical analytical method.
1. Introduction
Complexation Reactions
The following reaction between the metal ion Cd2+ and the ligand
NH3 is typical of a complexation reaction.
Cd2+ (aq) + 4:NH3 (aq) ↔ Cd(:NH3)42+ (aq)
The product of this reaction is a metal–ligand complex. In writing this

reaction we show ammonia as :NH3, using a pair of dots to
emphasize the pair of electrons that it donates to Cd2+.
1. Introduction
Metal-Ligand Formation Constants
We characterize the formation of a metal–ligand complex by a
formation constant, Kf. The complexation reaction between Cd2+ and
NH3, for example, has the following equilibrium constant.
The reverse of reaction Cd2+ (aq) + 4:NH3 (aq) ↔ Cd(:NH3)42+ (aq)

is a dissociation reaction, which we characterize by a dissociation
constant, Kd, that is the reciprocal of Kf.
1. Introduction
Many complexation reactions occur in a stepwise fashion. For
example, the reaction between Cd2+ and NH3 involves four successive
reactions.
Cd2+ (aq) + NH3 (aq) ↔ Cd(NH3)2+ (aq) (1)

Cd(NH3)2+ (aq) + NH3 (aq) ↔ Cd(NH3)22+ (aq) (2)
To avoid ambiguity, we divide formation constants into two categories.

A stepwise formation constant, which we designate as Ki for the ith
step, describes the successive addition of one ligand to the
metal–ligand complex from the previous step.
1. Introduction
Thus, the equilibrium constants for reactions (1)-(4) are, respectively,
K1, K2, K3, and K4. An overall, or cumulative formation constant, which
we designate as βi, describes the addition of i ligands to the free metal
ion. The equilibrium constant in equation below
is correctly identified as β4, where β4 = K1 x K2 x K3 x K4
In general
1. Introduction
Metal-Ligand Complexation and Solubility
A formation constant describes the addition of one or more ligands to a
free metal ion.
To find the equilibrium constant for a complexation reaction that
includes a solid, we combine appropriate Ksp and Kf expressions.
For example, the solubility of AgCl increases in the presence of excess
chloride ions as the result of the following complexation reaction.
AgCl (s) + Cl- (aq) ↔ Ag(Cl)2- (aq)
1. Introduction
Metal-Ligand Complexation and Solubility
We can write this reaction as the sum of three other equilibrium

reactions with known equilibrium constants—the solubility of AgCl,
which is described by its Ksp reaction
AgCl (s) ↔ Ag+ (aq) + Cl- (aq)
and the stepwise formation of AgCl2- , which is described by K1 and K2
reactions.
Ag+ (aq) + Cl- (aq) ↔ AgCl (aq)
AgCl (aq) + Cl- (aq) ↔ Ag(Cl)2- (aq)
The equilibrium constant for reaction AgCl (s) + Cl- (aq) ↔ Ag(Cl)2- (aq)
, therefore, is Ksp × K1 × K2.
1. Introduction
Example
Determine the value of the equilibrium constant for the reaction
PbCl2 (s) ↔ PbCl2 (aq)
Solution
We can write this reaction as the sum of three other reactions. The first
of these reactions is the solubility of PbCl2(s), which is described by its
Ksp reaction.
PbCl2 (s) ↔ Pb2 (aq) + 2Cl- (aq)
1. Introduction
Solution
The remaining two reactions are the stepwise formation of PbCl2(aq),
which are described by K1 and K2.
Pb2 (aq) + Cl- (aq) ↔ PbCl+ (aq)
PbCl+ (aq) + Cl- (aq) ↔ PbCl2 (aq)
Using values for Ksp, K1, and K2 from Appendix 10 and Appendix 12, we
find that the equilibrium constant is
K = Ksp x K1 x K2 = (2.0 x 10-19) x 38.9 x 1.62 = 0.93 x 10-17
2. Chemistry and Properties of EDTA
Ethylenediaminetetraacetic acid, or EDTA, is an
aminocarboxylic acid. EDTA, the structure of which
is shown in Figure 1a in its fully deprotonated form,
is a Lewis acid with six binding sites—the four
negatively charged carboxylate groups and the two
tertiary amino groups—that can donate up to six
pairs of electrons to a metal ion.
The resulting metal–ligand complex, in which EDTA
forms a cage-like structure around the metal ion
(Figure 1b), is very stable. The actual number of
coordination sites depends on the size of the metal
ion, however, all metal–EDTA complexes have a 1:1
stoichiometry. Figure 1.
Metal–EDTA Formation Constants
To illustrate the formation of a metal–EDTA complex, let’s consider the

reaction between Cd2+ and EDTA
Cd2+ (aq) + Y4- (aq) ↔ CdY2- (aq)
where Y4– is a shorthand notation for the fully deprotonated form of

EDTA shown in Figure 1a. Because the reaction’s formation constant
is large, its equilibrium position lies far to the right.
Kf: formation constant

EDTA is a Weak Acid
In addition to its properties as a ligand, EDTA is
also a weak acid.
The fully protonated form of EDTA, H6Y2+, is a
hexaprotic weak acid with successive pKa values
of
pKa1 = 0.0 pKa2 = 1.5 pKa3 = 2.0
pKa4 = 2.66 pKa5 = 6.16 pKa6 = 10.24
The first four values are for the carboxylic acid
protons and the last two values are for the
ammonium protons. Figure 9.27 shows a ladder
diagram for EDTA. The specific form of EDTA
(Y4-) is the predominate species only when the
pH is more basic than 10.24
Conditional Metal–Ligand Formation Constants
The formation constant for CdY2–assumes that EDTA is present as Y4
Because EDTA has many forms, when we prepare a solution of EDTA we
know it total concentration, CEDTA, not the concentration of a specific form,
such as Y4–.
To use equation, we need to rewrite it in terms of
CEDTA.
At any pH a mass balance on EDTA requires that its total concentration
equal the combined concentrations of each of its forms.
To correct the formation constant for EDTA’s acid–base properties we

need to calculate the fraction, α Y4– , of EDTA that is present as Y4–
Conditional Metal–Ligand Formation Constants
Table 1 provides values of αY4– for selected pH levels.
Solving equation for [Y4–] and substituting into
equation for the CdY2– formation constant
Table 1 and rearranging gives

Values of αY4– for Selected pH Levels
where Kf’ is a pH-dependent

conditional formation
constant.
EDTA Competes With Other Ligands
To maintain a constant pH during a complexation titration we usually add
a buffering agent.
If one of the buffer’s components is a ligand that binds with Cd2+, then
EDTA must compete with the ligand for Cd2+.
For example, an NH4+/NH3 buffer includes NH3, which forms several
stable Cd2+–NH3 complexes.
Because EDTA forms a stronger complex with Cd2+ than does NH3, it
displaces NH3; however, the stability of the Cd2+–EDTA complex
decreases.
We can account for the effect of an auxiliary complexing agent, such as
NH3, in the same way we accounted for the effect of pH. Before adding
EDTA, the mass balance on Cd2+, CCd, is
and the fraction of uncomplexed Cd2+, αCd2+,is
Solving for [Cd2+] and substituting into

Because the concentration of NH3 in a buffer essentially is constant,
we can rewrite this equation
to give a conditional formation constant, Kf”, that accounts for both pH

and the auxiliary complexing agent’s concentration. Table 2 provides
values of αM2+ for several metal ion when NH3 is the complexing agent.
Table 2 Values of αM2+ for Selected Concentrations of Ammonia

3. Complexometric EDTA Titration Curves
Now that we know something about EDTA’s chemical properties, we
are ready to evaluate its usefulness as a titrant.
To do so we need to know the shape of a complexometric titration
curve.
The analogous result for a complexation titration shows the change in
pM, where M is the metal ion’s concentration, as a function of the
volume of EDTA.
Step 1: Calculate the conditional formation constant for the
metal–EDTA complex.
Let’s calculate the titration curve for 50.0 mL of 5.00 × 10–3 M Cd2+
using a titrant of 0.0100 M EDTA. Furthermore, let’s assume the
titrand is buffered to a pH of 10 using a buffer that is 0.0100 M in
NH3.
Because the pH is 10, some of the EDTA is present in forms other
than Y4–. In addition, EDTA will compete with NH3 for the Cd2+.
To evaluate the titration curve, therefore, we first need to calculate
the conditional formation constant for CdY2–. . From Table 1 and
Table 2 we find that αY4– is 0.367 at a pH of 10, and that αCd2+ is
0.0881 when the concentration of NH3 is 0.0100 M.
Using these values, the conditional formation constant is
Kf”= Kf x α 4– x α 2+ = 2.9 x 1016 x 0.367 x 0.0881 =9.4 x 1014
Y Cd
Because Kf” is so large, we can treat the titration reaction

Cd2+ (aq) + Y4-(aq) → CdY2- (aq)
as if it proceeds to completion.
Step 2: Calculate the volume of EDTA needed to reach the equivalence point.
At the equivalence point we know that the moles of EDTA added

must equal the moles of Cd2+ in our sample; thus
Mol EDTA = MEDTA x VEDTA = MCd x VCd = mol Cd2+
Substituting in known values, we find that it requires
of EDTA to reach the equivalence point.

Step 3: Calculate pM values before the equivalence point by determining
the concentration of unreacted metal ions.
Before the equivalence point, Cd2+ is present in excess and pCd is

determined by the concentration of unreacted Cd2+.
Because not all unreacted Cd2+ is free—some is complexed with
NH3—we must account for the presence of NH3. For example, after
adding 5.0 mL of EDTA, the total concentration of Cd2+ is
To calculate the concentration of free Cd2+ we use equation
which gives a pCd of

Step 4: Calculate pM at the equivalence point using the conditional
formation constant.
At the equivalence point all Cd2+ initially in the titrand is now present
as CdY2–. The concentration of Cd2+, therefore, is determined by the
dissociation of the CdY2– complex.
First, we calculate the concentration of CdY2–.
Next, we solve for the concentration of Cd2+ in equilibrium with CdY2–.

Once again, to find the concentration of uncomplexed Cd2+ we must
account for the presence of NH3; thus
and pCd is 9.78 at the equivalence point.

Step 5: Calculate pM after the equivalence point using the conditional
formation constant.
After the equivalence point, EDTA is in excess and the concentration of

Cd2+ is determined by the dissociation of the CdY2– complex.
First, we calculate the concentrations of CdY2– and of unreacted EDTA.
For example, after adding 30.0 mL of EDTA the concentration of CdY2–
is
and the concentration of EDTA is
CEDTA = 6.25 x 10-4 M

Substituting into equation Kf”= Kf x αY4- x αCd2+ and solving for [Cd2+]
gives
CCd = 5.27 x 10-15 M

[Cd2+] = αCd2+ x CCd = (0.0881) (5.27 x 10-15 M) = 4.64 x10-16 M
a pCd of 15.33.
Table 3
Titration of 50.0 mL of 5.00x10-3 M Cd2+
with 0.0100 M EDTA at a pH of 10 and in
the Presence of 0.0100 M NH3
Figure 4 Titration curve for the

titration of 50.0 mL of 5.00×10–3 M
Cd2+ with 0.0100 M EDTA at a pH
of 10 and in the presence of
0.0100 M NH3. The red points
correspond to the data in Table 3.
The blue line shows the complete
titration curve.
The equivalence point of a complexation titration occurs when we
react stoichiometrically equivalent amounts of the titrand and titrant.
As is the case for an acid–base titration, we estimate the
equivalence point for a complexation titration using an experimental
end point.
A variety of methods are available for locating the end point,
including indicators and sensors that respond to a change in the
solution conditions.
Most indicators for complexation titrations are organic dyes—known
as metallochromic indicators—that form stable complexes with metal
ions.
The indicator, Inm–, is added to the titrand’s solution where it forms a
stable complex with the metal ion, MInn–.
As we add EDTA it reacts first with free metal ions, and then
displaces the indicator from MInn–.
MInn– (aq) + Y4- (aq) → MY2- (aq) + Inm– (aq)
If MInn– and Inm– have different colors, then the change in color signals
the end point.
The accuracy of an indicator’s end point depends on the strength of the
metal–indicator complex relative to the strength of the metal–EDTA
complex.
If the metal–indicator complex is too strong, the change in color occurs
after the equivalence point.
If the metal–indicator complex is too weak, however, the end point
occurs before we reach the equivalence point.
Most metallochromic indicators also are weak acids.
One consequence of this is that the conditional formation constant for
the metal–indicator complex depends on the titrand’s pH.
This provides some control over an indicator’s titration error because we
can adjust the strength of a metal–indicator complex by adjusted the pH
at which we carry out the titration.
Unfortunately, because the indicator is a weak acid, the color of the
uncomplexed indicator also may change with pH.
Figure 2, for example, shows the color of the indicator calmagite as a
function of pH and pMg, where H2In–, HIn2–, and In3– are different forms
of the uncomplexed indicator, and MgIn– is the Mg2+–calmagite
complex.
Because the color of calmagite’s metal–indicator complex is red, its
use as a metallochromic indicator has a practical pH range of
approximately 8.5–11 where the uncomplexed indicator, HIn2–, has a
blue color.
Figure 2 (a) Predominance diagram for the metallochromic indicator calmagite
showing the most important forms and colors of calmagite as a function of pH and
pMg, where H2In–, HIn2–, and In3– are uncomplexed forms of calmagite, and MgIn– is its
complex with Mg2+. Conditions to the right of the dashed line, where Mg2+ precipitates
as Mg(OH)2, are not analytically useful for a complexation titration. A red to blue end
point is possible if we maintain the titrand’s pH in the range 8.5–11. (b) Diagram
showing the relationship between the concentration of Mg2+ (as pMg) and the
indicator’s color. The ladder diagram defines pMg values where MgIn– and HIn– are
predominate species. The indicator changes color when pMg is between logKf – 1 and
logKf + 1.
Table 3 provides examples of metallochromic indicators and the metal
ions and pH conditions for which they are useful.
Even if a suitable indicator does not exist, it often is possible to
complete an EDTA titration by introducing a small amount of a
secondary metal–EDTA complex if the secondary metal ion forms a
stronger complex with the indicator and a weaker complex with EDTA
than the analyte.
Table 4 Selected Metallochromic Indicator

For example, calmagite has a poor end point when titrating Ca2+ with
EDTA.
Adding a small amount of Mg2+–EDTA to the titrand gives a sharper
end point.
Because Ca2+ forms a stronger complex with EDTA, it displaces Mg2+,
which then forms the red-colored Mg2+–calmagite complex. At the
titration’s end point, EDTA displaces Mg2+ from the Mg2+–calmagite
complex, signaling the end point by the presence of the uncomplexed
indicator’s blue form.
Selection and Standardization of Titrants
EDTA is a versatile titrant that can be used to analyze virtually all metal
ions.
Although EDTA is the usual titrant when the titrand is a metal ion, it
cannot be used to titrate anions, for which Ag+ or Hg2+ are suitable
titrants.
Solutions of EDTA are prepared from its soluble disodium salt,
Na2H2Y•2H2O, and standardized by titrating against a solution made
from the primary standard CaCO3.
Solutions of Ag+ and Hg2+ are prepared using AgNO3 and Hg(NO3)2,
both of which are secondary standards. Standardization is accomplished
by titrating against a solution prepared from primary standard grade
NaCl.
Inorganic analysis
Complexation titrimetry continues to be listed as a standard method for
the determination of hardness, Ca2+, CN–, and Cl– in waters and
wastewaters.
The determination of Ca2+ is complicated by the presence of Mg2+, which
also reacts with EDTA.
To prevent an interference the pH is adjusted to 12–13, which
precipitates Mg2+ as Mg(OH)2.
Titrating with EDTA using murexide or Eriochrome Blue Black R as the
indicator gives the concentration of Ca2+
Inorganic analysis
Cyanide is determined at concentrations greater than 1 mg/L by making
the sample alkaline with NaOH and titrating with a standard solution of
AgNO3 to form the soluble Ag(CN)2- complex.
The end point is determined using p-dimethylaminobenzalrhodamine as
an indicator, with the solution turning from a yellow to a salmon color in
the presence of excess Ag+.
Inorganic analysis
Chloride is determined by titrating with Hg(NO3)2, forming HgCl2(aq).
The sample is acidified to a pH of 2.3–3.8 and diphenylcarbazone,
which forms a colored complex with excess Hg2+, serves as the
indicator.
The pH indicator xylene cyanol FF is added to ensure that the pH is
within the desired range.
The initial solution is a greenish blue, and the titration is carried out to a
purple end point.
Quantitative Calculations
The quantitative relationship between the titrand and the titrant is
determined by the titration reaction’s stoichiometry.
For a titration using EDTA, the stoichiometry is always 1:1. Example 1
The concentration of a solution of EDTA is determined by standardizing

against a solution of Ca2+ prepared using a primary standard of CaCO3. A
0.4071-g sample of CaCO3 is transferred to a 500-mL volumetric flask,
dissolved using a minimum of 6 M HCl, and diluted to volume. After
transferring a 50.00-mL portion of this solution to a 250-mL Erlenmeyer
flask, the pH is adjusted by adding 5 mL of a pH 10 NH3–NH4Cl buffer that
contains a small amount of Mg2+–EDTA. After adding calmagite as an
indicator, the solution is titrated with the EDTA, requiring 42.63 mL to reach
the end point. Report the molar concentration of EDTA in the titrant.
Solution
The primary standard of Ca2+ has a concentration of
The moles of Ca2+ in the titrand is
8.135 x 10-3 M x 0.05000 L = 4.068 x 10-4 mol Ca2+
which means that 4.068×10–4 moles of EDTA are used in the titration.
The molarity of EDTA in the titrant is
Example 2
The concentration of Cl– in a 100.0-mL sample of water from a

freshwater aquifer is tested for the encroachment of sea water by
titrating with 0.0516 M Hg(NO3)2. The sample is acidified and titrated to
the diphenylcarbazone end point, requiring 6.18 mL of the titrant.
Report the concentration of Cl–, in mg/L, in the aquifer.
Solution
The reaction between Cl– and Hg2+ produces a metal–ligand complex of
HgCl2(aq). Each mole of Hg2+ reacts with 2 moles of Cl–; thus
are in the sample. The concentration of Cl– in the sample is

Evaluation of Complexation Titrimetry
The scale of operations, accuracy, precision, sensitivity, time, and cost of
a complexation titration are similar to those described earlier for
acid–base titrations.
Complexation titrations, however, are more selective. Although EDTA
forms strong complexes with most metal ion, by carefully controlling the
titrand’s pH we can analyze samples that contain two or more analytes.
The reason we can use pH to provide selectivity is shown in Figure
9.34a. A titration of Ca2+ at a pH of 9 has a distinct break in the titration
curve because the conditional formation constant for CaY2– of 2.6 × 109
is large enough to ensure that the reaction of Ca2+ and EDTA goes to
completion. At a pH of 3, however, the conditional formation constant of
1.23 is so small that very little Ca2+ reacts with the EDTA.
Evaluation of Complexation Titrimetry
Suppose we need to analyze a mixture of Ni2+ and Ca2+. Both analytes
react with EDTA, but their conditional formation constants differ
significantly.
If we adjust the pH to 3 we can titrate Ni2+ with EDTA without titrating
Ca2+ (Figure 9.34b). When the titration is complete, we adjust the
titrand’s pH to 9 and titrate the Ca2+ with EDTA.
Figure 3 Titration curves illustrating how we can use the titrand’s pH to
control EDTA’s selectivity. (a) Titration of 50.0 mL of 0.010 M Ca2+ at a pH of
3 and a pH of 9 using 0.010 M EDTA. At a pH of 3 the CaY2– complex is too
weak to titrate successfully. (b) Titration of a 50.0 mL mixture of 0.010 M
Ca2+ and 0.010 M Ni2+ at a pH of 3 and at a pH of 9 using 0.010 M EDTA. At
a pH of 3 EDTA reacts only with Ni2+. When the titration is complete, raising
the pH to 9 allows for the titration of Ca2+.
Representative Method
Determination of Hardness of Water and Wastewater
Description of the Method
The operational definition of water hardness is the total
concentration of cations in a sample that can form an
insoluble complex with soap.
Although most divalent and trivalent metal ions contribute to
hardness, the two most important metal ions are Ca2+ and
Mg2+.
Hardness is determined by titrating with EDTA at a buffered
pH of 10. Calmagite is used as an indicator. Hardness is
reported as mg CaCO3/L.
Procedure
Select a volume of sample that requires less than 15 mL of
titrant to keep the analysis time under 5 minutes and, if
necessary, dilute the sample to 50 mL with distilled water.
Adjust the sample’s pH by adding 1–2 mL of a pH 10 buffer
that contains a small amount of Mg2+–EDTA.
Add 1–2 drops of indicator and titrate with a standard
solution of EDTA until the red-to-blue end point is reached
Figure 4 End point for the titration of hardness with EDTA using calmagite as
an indicator; the indicator is: (a) red prior to the end point due to the presence
of the Mg2+–indicator complex; (b) purple at the titration’s end point; and (c)
blue after the end point due to the presence of uncomplexed indicator.
Questions
1. Why is the sample buffered to a pH of 10? What problems might you
expect at a higher pH or a lower pH?
Of the two primary cations that contribute to hardness, Mg2+ forms the
weaker complex with EDTA and is the last cation to react with the titrant.
Calmagite is a useful indicator because it gives a distinct end point when
titrating Mg2+ (see Table 4).
Because of calmagite’s acid–base properties, the range of pMg values over
which the indicator changes color depends on the titrand’s pH (Figure 2).
Figure 4 shows the titration curve for a 50-mL solution of 10–3 M Mg2+ with
10–2 M EDTA at pHs of 9, 10, and 11.
Superimposed on each titration curve is the range of conditions for which
the average analyst will observe the end point. At a pH of 9 an early end
point is possible, which results in a negative determinate error. A late end
point and a positive determinate error are possible if the pH is 11.
Figure 4 Titration curves for 50 mL of 10–3 M Mg2+ with 10–3 M EDTA
at pHs 9, 10, and 11 using calmagite as an indicator. The range of
pMg and volume of EDTA over which the indicator changes color is
shown for each titration curve.
2. Why is a small amount of the Mg2+–EDTA complex added to the buffer?
The titration’s end point is signaled by the indicator calmagite.
The indicator’s end point with Mg2+ is distinct, but its change in color when
titrating Ca2+ does not provide a good end point (see Table 4).
If the sample does not contain any Mg2+ as a source of hardness, then the
titration’s end point is poorly defined, which leads to an inaccurate and
imprecise result.
Adding a small amount of Mg2+–EDTA to the buffer ensures that the titrand
includes at least some Mg2+.
Because Ca2+ forms a stronger complex with EDTA, it displaces Mg2+ from the
Mg2+–EDTA complex, freeing the Mg2+ to bind with the indicator.
This displacement is stoichiometric, so the total concentration of hardness
cations remains unchanged. The displacement by EDTA of Mg2+ from the
Mg2+–indicator complex signals the titration’s end point.
3. Why does the procedure specify that the titration take
no longer than 5 minutes?
A time limitation suggests there is a kinetically-controlled
interference, possibly arising from a competing chemical
reaction.
In this case the interference is the possible precipitation of
CaCO3 at a pH of 10
1. EDTA is the abbreviation of……..
a. Nitril triacetic acid
b. Ethylenediaminetetraacetic acid
c. Aminopolycarboxylic acid derivative
d. Disodium ethylenediaminetetraacetic
2. EDTA is a……
a. Strong acid
b. Strong base
c. Weak acid
d. Weak base
3. The specific form of EDTA as Y4- is the predominate
species only when the pH is more basic than…...
a. 10.24
b. 9.16
c. 8.32
d. 8.50
4. At the pH of 4-6, EDTA has a form of
a. H 5Y +
b. H2Y2-
c. HY3-
d. H 3Y -
5. Metallochromic indicatora are those which change their
colors depend on……
a. The protonated form of EDTA
b. The formation constant
c. The conditional formation constant
d. The concentration of EDTA
6. The determination of Ca2+ by titrating with EDTA using……as
indicator
a. Eriochrome Blue Black B
b. Eriochrome Black T
c. Murexide
d. Salicylic acid
7. The determination of Ca2+ is complicated by the
presence of Mg2+, which also reacts with EDTA. To
prevent an interference the pH is adjusted to……
a. 7-8
b. 8-9
c. 12-13
d. 9-10
8. p-dimethylaminobenzalrhodamine as an indicator for cyanide
determination in an alkaline solution has a color of……in the
presence of excess Ag+
a. Yellow
a. Salmon color
b. Red
c. Purple
9. Solutions of EDTA are standardized by titrating
against a solution made from the primary standard…….
a. CaCO3
b. NaCl
c. Benzoic acid
d. KHCO3
Practice Exercise
A 100.0-mL sample is analyzed for hardness using

the procedure outlined in Representative Method,
requiring 23.63 mL of 0.0109 M EDTA. Report the
sample’s hardness as mg CaCO3/L.
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Evaluating Analytical Data
Characterizing Measurements and Results
Mean 𝑿, is the numerical average obtained by dividing

the sum of the individual measurements by the number
of measurements
x1  x2  ...  xn

n
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Median (𝑋med).
The data from the smallest to the largest value
3.056 3.080 3.094 3.107 3.112 3.174 3.198 the median is
3.107
Range
Range = w = Xlargest – X smallest
Standard Deviation
Relative standard deviation
SD
% RSD  x100
xmean
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Example 1: What are the standard deviation, the

relative standard deviation, and the percent relative
standard deviation for the data 3.056 3.080 3.094 3.107
3.112 3.174 3.198
Variance: The square of the standard deviation
Characterizing Experimental Errors
Accuracy
Accuracy is usually expressed as either an absolute error
E = X–µ
Determinate error: can be traced to an identifiable

source.
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Characterizing Experimental Errors
 Sampling error An error introduced during the

process of collecting a sample for analysis.
 Heterogeneous Not uniform in composition.
 Method error An error due to limitations in the
analytical method used to analyze a sample.
 Measurement error An error due to limitations in the
equipment and instruments used to make
measurements
 Tolerance The maximum determinate measurement
error for equipment or instrument as reported by the
manufacturer.
Precision
hight low
low
precision
and
accuracy
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Precision
 Repeatability The precision for an analysis in which

the only source of variability is the analysis of
replicate samples.
 Reproducibility The precision when comparing
results for several samples, for several analysts
or several methods.
 indeterminate error Any random error that causes
some measurements or results to be too high
while others are too low
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Sources of Indeterminate Error
Can be traced to several sources,

- The collection of samples,
- The manipulation of samples during
- The analysis
- The making of measurements
Evaluating Indeterminate Error
Indeterminate errors may be estimated by an appropriate

measure of spread
Uncertainty The range of possible values for a

measurement
Uncertainty When Adding or Subtracting
the equations R = A + B + C or R = A + B – C, or
any other combination of adding and subtracting A, B,
and C, the absolute uncertainty in R is
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Example
The class A 10 mL pipet characterized in Table 4.2 is used

to deliver two successive volumes. Calculate the absolute
and relative uncertainties for the total delivered volume.
SOLUTION
The total delivered volume is obtained by adding the
volumes of each delivery; thus Vtot = 9.992 mL + 9.992
mL = 19.984 mL Using the standard deviation as an
estimate of uncertainty, the uncertainty in the total
delivered volume is
Example
Thus, we report the volume and its absolute uncertainty

as 19.984 ± 0.008 mL.
The relative uncertainty in the total delivered volume is
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Uncertainty When Multiplying or Dividing
The equations R = A × B × C or R = A × B/C, or any other

combination of multiplying and dividing A, B, and C, the
relative uncertaintyin R is
Example
The quantity of charge, Q, in coulombs passing through
an electrical circuit is Q = I × t
where I is the current in amperes and t is the time in
seconds. When a current of 0.15 ± 0.01 A passes
through the circuit for 120 ± 1 s, the total charge is Q =
(0.15 A) × (120 s) = 18 C
Calculate the absolute and relative uncertainties for the
total charge.
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SOLUTION
Since charge is the product of current and time, its
relative uncertainty is
The absolute uncertainty in the charge is

sR = R × 0.0672 = (18) × (±0.0672) = ±1.2
Thus, we report the total charge as 18 C ± 1 C.
Confidence Intervals for Populations
Confidence interval Range of results around a mean value

that could be explained by random error
true mean value
population’s variance,
confidence interval
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Example
 What is the 95% confidence interval for the amount of
aspirin in a single analgesic tablet drawn from a
population where µ is 250 mg and σ2 is 25?
 SOLUTION
The 95% confidence interval for a single member of a
normally distributed population is
Xi = µ ± 1.96σ = 250 mg ± (1.96)(5) = 250 mg ± 10 mg
Thus, we expect that 95% of the tablets in the
population contain between 240 and 260 mg of aspirin.
Confidence Intervals for Populations
 Degrees of Freedom Unlike the population’s

variance, the variance of a sample includes the term
n – 1 in the denominator, where n is the size of the
sample
 Confidence Intervals for Samples
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t-Student
Degrees of 0.1 (90 %) 0,05 (95 %) 0,02 (98%) 0,01 (99%)
freedom
1 6,31 12,71 31,82 63,66
2 2,92 4,30 6,96 9,92
3 2,35 3,18 4,54 5,84
4 2,13 2,78 3,75 4,60
5 2,02 2,57 3,36 4,03
6 1,94 2,45 3,14 3,71
7 1,89 2,36 3,00 3,50
8 1,86 2,26 2,90 3,25
9 1,83 2,23 2,76 3,17
10 1,81 2,18 2,68 3,05
Statistical Methods for Normal Distributions
 Null hypothesis, H0,

Retained if the significance test does not fail (H0).
 Alternative hypothesis
accepted if the significance test shows that null hypothesis
should be rejected (HA)
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 Comparing X— to µ
The equation for the test (experimental) statistic, t
exp, is derived from the confidence interval for µ
Comparing X— to µ
t-test
Statistical test for comparing
two mean values to see if
their difference is too large
to be explained by
indeterminate error.
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Example
Before determining the amount of Na2CO3 in an unknown
sample, a student decides to check her procedure by analyzing a
sample known to contain 98.76% w/w Na2CO3. Five replicate
determinations of the %w/w Na2CO3 in the standard were made
with the following results 98.71% 98.59% 98.62% 98.44%
98.58%. Is the mean for these five trials significantly different
from the accepted value at the 95% confidence level (α = 0.05)?
 Comparing s2 to σ2
F-test: Statistical test for comparing two variances to see
if their difference is too large to be explained by
indeterminate error.
 A critical value, F(α, νnum, νden), gives the largest value

of F that can be explained by indeterminate error.
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Example
A manufacturer’s process for analyzing aspirin tablets has
a known variance of 25. A sample of ten aspirin tablets is
selected and analyzed for the amount of aspirin, yielding
the following results:
254; 249; 252; 252; 249; 249; 250; 247; 251; 252
Determine whether there is any evidence that the
measurement process is not under statistical control at α =
0.05.
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 Comparing Two Sample Variances
The F-test can be extended to the comparison of
variances for two samples, A and B,
 sA2 = 0.00259
 and sB2 = 0.00138
 F (0.05, 6, 4) is 9.197; Fexp is less than F (0.05, 6, 4), the null
hypothesis is retained. There is no evidence at the
chosen significance level to suggest that the difference
in precisions is significant.
Fisher (F-test)
B\A 1 2 3 4 5 6 7 8 9
1 647.8 799.5 864.2 899.6 921.8 937.1 948.2 956.7 963.3
2 38.51 39.0 39.17 39.25 39.30 39.33 39.36 39.377 39.39
3 17.44 16.04 15.44 15.10 14.88 14.73 14.62 14.54 14.47
4 12.22 10.65 9.979 9.605 9.364 9.197 9.074 8.980 8.905
5 10.01 8.434 7.764 7.388 7.146 6.978 6.853 6.757 6.681
6 8.813 7.260 6.599 6.227 5.988 5.820 5.695 5.600 5.523
7 8.073 6.542 5.890 5.523 5.285 5.119 4.995 4.899 4.823
8 7.571 6.059 5.416 5.053 4.817 4.652 4.529 4.433 4.357
9 7.209 5.715 5.078 4.718 4.484 4.320 4.197 4.102 4.026
10 6.937 5.456 4.826 4.468 4.236 4.072 3.950 3.855 3.779
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Comparing Two Sample Means (t-test)
Confidence intervals for

µA and µB
Equal varian
t exp is compared with a critical value, t (α, ,), as determined

by the chosen significance level, , the degrees of freedom
for the sample, 
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 Unequal varian
 the degrees of freedom is calculated
 The null hypothesis is rejected if t exp is greater than

 t (α, ν), and retained if t exp is less than or equal to t (α, ν).
Example
 The %w/w Na2CO3 in soda ash can be determined
by an acid–base titration. The results obtained by
two analysts are shown here. Determine whether the
difference in their mean values is significant at α =
0.05.

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 The null and alternative hypotheses are
 The degrees of freedom are calculated
Outliers : The Q-test compares the difference between

the suspected outlier and its nearest numerical neighbor
to the range of the entire data set
Dixon’s Q-test: Statistical test for deciding if an outlier

can be removed from a set of data.
 the suspected outlier

is the smallest value (X1)
 the suspected outlier is

the largest value (Xn)
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Example
 The following to determine the content KMnO4 :
 3.067; 3.049; 3.039; 2.514; 3.048; 3.079; 3.094
3.109; 3.102 g/L
 Determine if the value of 2.514 g is an outlier at α =
0.05.
Solution
 place the masses in order from smallest to
largest : 2.514; 3.039; 3.048; 3.049; 3.067
3.079; 3.094; 3.102; 3.109
calculate Qexp
 Q (0.05, 9) is 0.493. Since Q exp > Q (0.05, 9) the

value is assumed to be an outlier, and can be
rejected.
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Case study
 Shown in the following rows are results for the
determination of acetaminophen (mg) in 10 separate tablets
224.3; 240.4; 246.3; 239.4; 253.1; 261.7; 229.4, 255.5
235.5; 249.7
(a) Report the mean, median, range, standard deviation, and
variance for these data.
 (b) Assuming that 𝑋 and s2 are good approximations for µ
and σ2, and that the population is normally
distributed, what percentage of tablets are expected to
contain more than the standard amount of 250 mg
acetaminophen per tablet
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Case study
 Alexiev and associates describe an improved photometric
method for the determination of Fe3+ based on its catalytic
effect on the oxidation of sulphanilic acid by KIO4.29
 Determine whether there is a significant difference between

the two methods at α = 0.05
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Units for expressing concentration

Converting between concentration units
Buffer solutions- Volumetric solutions
Assoc. Pro. Hà Diệu Ly
UNITS FOR EXPRESSING CONCENTRATION
Concentration is a general measurement unit stating

the amount of solute present in a known amount of
solution
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Percent concentration mct

mct : grams of solute C %(W / W )  100%
V .d
C %.mdd C %.V .d
m 
100 100
d  d H 2O  1 ( g / ml )
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Example 1:
A solution in which a solute has a concentration of 23%
w/v contains 23 g of solute per 100 mL of solution.
23
C%  100  23%
100
Example 2: Calculate natri clorid to dilute 3000ml of
10% natri clorid solution?
mct C %.Vdd 10 x3000
C%  100  mct    300( g )
Vdd 100 100
Example: Calculate the V of 37,23% hydrochloric acid

solution (d = 1,19) required to prepare 100 ml of 10 %
HCl solution (W/ V
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Solution
Weigh of pure HCL in 100ml of 10% HCl solution (gam)
m ct C (%)xVdd 10 x100
C %(kl / tt ) = × 100%  mct    10
V dd 100 100
The V of 37,23% HCl solution transfer (ml):
mct mct 10
C %(kl / kl )  100%  Vdd   100%  x100%  22,5
V .d d .C (%) 1,19 x37,23
Transfer 22.5 ml of 37.23 % HCl solution to make 100 ml of

distilled to get 10 % HCl solution
Some cases: a solution in which m(g) of solute is dissolved

in b(g) of solvent
m
C %(w / w)  100
mb
Example 3: 0.25g is dissolved in 100ml of water, the C%
(kl/kl) concentration of Alizarin is
m 0,25
C %(w / w)   100  0,249%
m  b 0,25  100
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Volume percent: milliliters of solute per 100 mL of

solution (% v/v)
V
C %(V / V )  s 100%
Vdd
Example 4: Transfer 960ml absolute ethanol dissolve to

1000ml solution. The concentration of this solution is
960
C %(V / V )  100%  96%
1000
Molarity and Formality

Molarity: The number of moles of solute per liter
of solution (M).
n
CM 
V
m
n  CM 
m
x1000
M M .V
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 Equivalent The moles of a species that can donate

one reaction unit.
 n = 2 for Pb2+ and n = 1 for I–.

In an acid–base reaction, the reaction unit is the number
of H+ ions donated by an acid or accepted by a base
 n = 2 for H2SO4 and n = 1 for NH3

For a complexation reaction, the reaction unit is the
number of electron pairs that can be accepted by the
metal or donated by the ligand
Ag+ is 2 and that for NH3 is 1
In an oxidation–reduction reaction the reaction unit is
the number of electrons released by the reducing agent
or accepted by the oxidizing agent
 n = 1 for Fe3+ and n = 2 for Sn2+
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 Equivalent weight:The mass of a compound

containing one equivalent (EW).
 Formula weight:The mass of a compound
containing onemole (FW).
 Equivalent weights (EW) per unit volume and, like
formality, is independent of speciation
 An equivalent weight is defined as the ratio of a

chemical species’ formula weight (FW) to the
number of its equivalents
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Example 5:
NaOH solution contain 4g of pure NaOH to dilute 1000
ml (M = 40g).
Weight of NaOH : m = 4g
Molarity of NaOH : M = 40g
Volumne of disolled : V = 1000ml
m 4
CM 
M .V
x1000  CM 
40x1000
x1000  0,1M
Example 6 : Calculate the molarity of the H2SO4 solution,

knowing that to make a solution with a volume of 500ml,
49 g of concentrated H2SO4 is required. Molarity of H2SO4
(M = 98 grams)
 Weight of H2SO4: m = 49g
 Molarity: M = 98g
 volume of required V = 500ml
m 49
CM  .1000  x1000  1( M )
M .V 98x500
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Example 7: 2,7g NaCl in 100ml solution. Calculate

concentration of NaCl solution.
m 2,7
CM  .1000  x1000  0,46( M )
M .V 58,5 x100

 Normality
The number of equivalents of solute per liter of
solution (N). The number of equivalents, n, is based
on a reaction unit
mct
CN  .1000
E.Vdd
 Equivalent weight: The mass of a compound
containing one equivalent (E)
N  n*M
 Formula weight: The mass of a compound containing
one mole (M).
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Example 7 . Calculate the equivalent weight and

normality for a solution of 6.0 M H3PO4 given the
following reactions:
Example 8: Calculate the equivalent concentration of

AgNO3 solution (M = 108), when 1.35g AgNO3 is
dissolved in water to form 250ml of solution
Molarity of AgNO3: M = 170g/mol.

Solution : V = 250ml.
Ag+ = 1 EW= FW of AgNO3:
m 1.35
CN  .1000  x1000  0.03N
Ex.V 170 x 250
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CONVERTING BETWEEN CONCENTRATION UNITS
 The units of concentration most frequently

encountered in analytical chemistry are
molarity, weight percent, volume percent, weight-to-
volume percent
Example 10. A concentrated solution of aqueous

ammonia is 28.0% w/w NH3 and has a density of 0.899
g/mL. What is the molar concentration of NH3 in this
solution?
Solution
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Example 11 : Determine the weight of 20% NaOH

solution that needs to be added to 1000g of water to obtain
a 5% NaOH solution
ma c  b m NaOH c  b
 

mb a  c mH 2O a  c
m NaOH, a = 20%
m Pure Water = 1000g, b = 0
obtained NaOH solution: c = 5%
cb 50
mNaOH  xmH 2O  x1000  333,3g
ac 20  5
To prepare lower concentrations from strong

concentration
Mix a% solution with b% solution (of the same substance)
to get a c% solution with a > c > b if a > b.
The ratio is calculate by the diagonal rule
a (c – b) = ma
ma c  b
c  
mb a  c
b (a – c) = mb
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Relationship between some common concentrations
m m
CM 
m
.1000 CN  .1000 C %(kl / kl )  ct  100
M .V Ex.V d .V dd
Relationship exists between normality and molarity
CN
CM   C N  n.C M
n
Example 12.
C2H5OH + K2Cr2O7 + H2SO4  CH3CHO +Cr2(SO4)3 +
K2SO4 + H2O.
The concentraion of 3M of K2Cr2O7 solution is ?
Number of electrons exchanged: 2Cr 6+ - 6e  2Cr 3+
C N  n.CM  6 x3  18
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Relationship between of CM and C% :

10.C %.d C .M
CM   C%  M
M 10.d
Example: Calculate CM of 10% NaOH solution, (dNaOH

10% =1,10). 10 x10 x1,1
CM   2,75M
40
.
 Example 13 : Calculate C% of 14,8M NH4OH

solution (d = 0,899g/ml, M = 17,03g/l)
C M .M 14,8 x17,03
C%  C%   28,03%
10.d 10 x0,899
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 Example 14: Calculate CN of 14.35% (d = 1.1g/ml)

sulfuric acid solution.
 Solution
C (%).d 14.35x1.1
CN  .10 CN  .10  3.22 N
E 49
 Example 15: 200 ml of 0.25 M NH3 solution to be
diluted from 28% of NH3 (d=0.899g/ml)?
10.C %.d 10 x 28 x0,899
CM   CM   14,8M
M 17,03
 Relationship between CM and Pg/l:

Pg / l  M .C M
 Relationship between CN and Pg/l:
Pg / l  E.C N
 Relationship between C% and Pg/l:
Pg / l  10.d.C%
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Preparing Solutions by Dilution

Co.Vo = C1V1
Co, Vo is the concentration and volume of the stock solution
C1, V1 is the concentration and volume of the dilute
solution.
Calculating reaction
CNA.VA  CNB .VB
Example 15: A laboratory procedure calls for 250 mL of an

approximately 0.10 M solution of NH3. Describe how you
would prepare this solution using a stock solution of
concentrated NH3 (14.8 M).
Solution: 14.8 M. Vo = 0.10 M. 0.25 L
Vo gives 1.69 × 10–3 L, or 1.7 mL
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Example 16: A laboratory procedure calls for 1000 mL of

an approximately 0.10 N solution of HCl. Describe how
you would prepare this solution using a stock solution
of concentrated HCL (12.1 N).
Co .Vo  C1.V1

C1.Vl 0,1x1000
Vo    8,26ml
C0 12,1
BUFFER SOLUTIONS
A solution containing a conjugate weak acid/weak base pair

that is resistant to a change in pH when a strong acid or strong
base is added
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BUFFER SOLUTIONS
The relationship between the pH of an acid–base buffer and

the relative amounts of CH3COOH and CH3COO– is derived
by taking the negative log of both sides
BUFFER SOLUTIONS
USES: Buffers are used to establish and maintain an

ion activity within narrow limits.
The most common systems are used for the following:
- To establish hydrogen-ion activity for the calibration of pH

meters in the preparation of dosage forms that approach
isotonicity in analytical procedures to maintain stability of
various dosage forms
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BUFFER SOLUTIONS
 Preparation Previously dry the crystalline reagents at

110°–120° for 1 h, except for boric acid and sodium
acetate trihydrate.
 Where water is specified for solution or dilution of test
substances in pH determinations, use carbon dioxide-
free water.
 Store the prepared solutions in chemically resistant,
tight containers such as Type 1 glass bottles. Use the
solutions within 3 months.
BUFFER SOLUTIONS
STANDARD BUFFER SOLUTIONS

Standard solutions of definite pH are readily available in buffer
solutions prepared from the appropriate reagents.
Buffer solutions, buffer tablets, and buffer solids may be
obtained from commercial sources in convenient prepackaged
form.
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VOLUMETRIC SOLUTIONS
 by accurately weighing/dilute a suitable quantity of
the chemical/strong concentration and dissolving it
to produce a specific volume of solution of known
concentration
 Correction factor:
The correction factor so obtained is used in all
calculations where such solutions are used
 The concentration of the volumetric solution does
not differ from the prescribed one by more than
10%.
 The repeatability does not exceed 0.2% (relative
standard deviation). The correction factor should be
redetermined frequently.
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Preparation and standardization
 Preparation by dilution: to prepare lower
concentrations accurately by making an exact dilution
of a stronger solution.
 Dilute solutions that are not stable are preferably
prepared
 Preparation by standardization of volumetric solutions
 Preparation by accurately weighing of chemical PA
Example 16.
0.1 N Hydrochloric Acid VS, from 36.46%
hydrochloric acid
 3.646 g in 1000 mL
Dilute 8.5 mL of hydrochloric acid with water to 1000
mL.
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 Standardization:Accurately weigh about 0.5 g

of tromethamine, dried according to the label
instructions or, if this information is not available, dried
at 105° for 3 h. Dissolve in 50 mL of water, and add 2
drops of bromocresol green
 Titrate with 0.1 N hydrochloric acid to a pale yellow
endpoint. Each 12.114 mg of tromethamine is equivalent
to 1 mL of 0.1 N hydrochloric acid
Example 17. Dilute 100.0 ml of 0.10 N H2C2O4 solution
from the primary substance H2C2O4.2H2O
M
EH 2 C 2 O4 .2 H 2 O   63,03
2
m
CN  .1000
Ex.V
CN .E.V 0,1.63,03.100
mH 2C2O4 .2 H 2O    0,6303g
1000 1000
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 Correction factor K
Standardization with primary standard
a is weight of primary standard

T is the theoretical titration of the primary standard (g/ml)
V is the number of ml of titration solution used.
M is Molecular mass of
the substance to be titrated m
Tg / ml 
1000
Standardization with a known titration solution (Ko)
Co, Vo is the theoretical concentration and the number of the

titration solution used for standardization
C is the theoretical concentration of the titration solution to
be prepared
V is the number of ml of titrant solution to be used to
determine the K factor.
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If K is outside the specified range, the solution should be
diluted or concentrated
 K>1 dilution is required
the number of ml of solvent to be added to 1000 ml of

solution = (K - 1) .1000
 K< 1: add the chemical primary PA

the number of grams of chemical that must be added to
1000 ml of the solution = (1-K).1000
Case study
1. Determine the K factor of 0.1 N NaOH solution with
potassium hydrophthalate C8H5O4K as 1.08. Let's
adjust the K factor to the allowable range. Indicates
that 500 ml of NaOH has been prepared and 30 ml has
been used up for titration.
2. Determine the K factor of 0.1 N NaOH solution with
potassium hydrophthalate C8H5O4K as 0.95. Let's
adjust the K factor to the allowable range. Indicates
that 500 ml of NaOH has been prepared and 30 ml has
been used up for titration.
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Analytical Chemistry- Drug Quality control
Gravimetric Methods
of Analysis
Assoc. Prof. Hà Diệu Ly
Gravimetric analysis:
Gravimetry: Any method in which the signal is a mass

or change in mass.
a quantitative method for accurately determining the

amount of substance by selective precipitation of the
substance from an aqueous solution
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Types of Gravimetric Methods

- Precipitation gravimetry: A gravimetric method in which
the signal is the mass of a precipitate.
-Volatilization gravimetry: A gravimetric method in

which the loss of a volatile species gives rise to the signal.
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- Particulate gravimetry: removal from the sample

matrix by filtration or extraction.
- Electrogravimetry: deposit the analyte as a solid film

an electrode in an electrochemical cell.
Precipitation Gravimetry
 The precipitate must be of low solubility, high purity,
and of known composition.
 The precipitate must be in a form that is easy to
separate from the reaction mixture
BaCl2 + Na2SO4 = BaSO4 ↓ + 2NaCl
Precipitate formed : BaSO4, precipitate is also

isolated and heated, weighed,
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 Solubility consideration
 Controlling particle size: Larger particles are
easier to filter
 Filtering the precipitate
- The precipitate must have a low solubility
- The precipitate must be of high purity
- The precipitate requires large crystals
- The precipitate converte to a precipitat weighed
Filter paper is rated as fast (retains particles

larger than 20–25 mm), medium–fast (retains particles
larger than 16 mm), medium (retains particles larger
than 8 mm), and slow (retains particles larger than 2–3
mm)
- Avoiding impurities: by heating in a small portion of
a suitable solvent to dissolve
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Precipitate weighted
- Must be stable in the
environment
- do not absorb moisture or
decompose
- F corresponds to the balance
form as small as possible
Rinsing the precipitate
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Rinsing the precipitate
Drying the precipitate

- Placing the precipitate in a laboratory oven and heating to
a temperature of 110 oC is sufficient when removing water
and other easily volatilized impurities.
- Fritted-glass crucibles can not withstand high
temperatures and must be dried in an oven at temperatures
below 200 oC.
- The glass fiber mats used in Gooch crucibles can be
heated to a maximum temperature of approximately 500 oC
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P.F
C (%)w / v  .100
V
Example . 0.825 g of FeCl3 solution was diluted with

water and the precipitated as Fe(OH)3 by NaOH solution.
After filtering and rinsing, the residue was ignited, giving
0.8525 g of pure Fe2O3. Calculate the %w/w Fe in the
sample.
3NaOH + FeCl3 = Fe(OH)3 ↓ + 3NaCl

2Fe(OH)3  Fe2O3 ↓ + 3H2O
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
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Calculate g amount of Fe(NO3)3. H2O in sample
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Example
Cr 3+ (Cr=52) Cr2O3
BaCrO4
Compare to 2 precipitate formed and select the precipitant ?
Solution
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Volatilization Gravimetry
Thermogravimetry: A form of volatilization gravimetry

in which the change in a sample’s mass is monitored while
it is heated.
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Example
The thermogram in Figure shows the change in mass for a
sample of calcium oxalate monohydrate, CaC2O4 ⋅ H2O.
The original sample weighed 24.60 mg and was heated
from room temperature to 1000 °C at a rate of 5 °C min.
The following changes in mass and corresponding
temperature ranges were observed:
Loss of 3.03 mg from 100–250 °C
Determine the identities of the volatilization products and the
solid residue at each step of the thermal decompotion
Example
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Solution
 The loss of 3.03 mg from 100–250 °C corresponds to a
12.32% decrease in the original sample’s mass.
In terms of CaC2O4⋅ H2O, this corresponds to a loss of 18.00

g/mol
Solution
The loss of 4.72 mg from 400–500 °C represents a
19.19% decrease in the original mass of 24.60 g, or a loss
of
This loss is consistent with CO as the volatile product,

leaving a residue of CaCO3. Finally, the loss of 7.41 mg
from 700–850 °C is a 30.12% decrease in the original
mass of 24.60 g. This is equivalent to a loss of
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Equipment
- A laboratory oven or a muffle furnace,
- The weight of the sample and the solid residue are
determined using an analytical balance.
The most frequently encountered example of a direct
volatilization gravimetric analysis is the determination
of a compound’s elemental composition.
Example
A sample of slag from a blast furnace is analyzed for

SiO2 by decomposing a 0.5003 g sample with HCl,
leaving a residue with a mass of 0.1414 g. After treating
with HF and H2SO4 and evaporating the volatile SiF4, a
residue with a mass of 0.0183 g remains. Determine the
%w/w SiO2 in the sample.
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Solution
In this procedure the difference in the residue’s mass
before and after volatilizing SiF4 gives the mass of SiO2 in
the sample. Thus the sample contained
The %w/w SiO2, therefore, is
Example: A 26.23 mg sample of MgC2O4 • H2O and

inert materials is heated to constant weight at 1200 °C,
leaving a residue weighing 20.98 mg. A sample of pure
MgC2O4 • H2O, when treated in the same fashion,
undergoes a 69.08% change in its mass. Determine the
%w/w MgC2O4 • H2O in the sample.
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SOLUTION
The change in mass when analyzing the mixture is 5.25
mg, thus the grams of MgC2O4 • H2O in the sample is
The %w/w MgC2O4 • H2O, therefore, is
Evaluating Volatilization Gravimetry

Indirect analysis:
- Sensitivity can be improved by carefully choosing the
conditions for combustion or volatilization so that the
change in mass is as large as possible
- Direct volatilization gravimetric methods: the analyte is
a gaseous product retained in an absorbent trap
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Particulate Gravimetry
- Filtration: solid particulates are separated from their

gas, liquid, or solid matrix
- Filters are constructed from a variety of materials,
including cellulose fibers pore size from 30 µm to 2–3
µm
- Glass fibers: pore size from 2.5 µm to 0.3 µm
- Membrane filters : cellulose nitrate, and
polytetrafluoroethylene (PTFE) with pore sizes from 5.0
µm to 0.1 µm.
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- Liquid-phase or solid-phase extraction:
Poorly filterable solids if the analyte can be extracted
from its matrix with a suitable solvent
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After extraction, the solvent can be evaporated and the mass

of the extracted analyte determined
After filtering and drying the filter to constant weight at
103–105 °C.
The result of a quantitative analysis by particulate
gravimetry is just the ratio, using appropriate units, of
the amount of analyte to the amount of samp
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Example
A 200.0 mL sample of water was filtered through a

preweighed glass fiber filter. After drying to constant
weight at 105 °C, the filter was found to have increased
in mass by 48.2 mg. Determine the total suspended
solids for the sample in parts per million.
SOLUTION
Parts per million is the same as milligrams of analyte

per liter of solution; thus, the total suspended solids for
the sample is
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Evaluating Particulate Gravimetry
Particulate gravimetric methods based on filtration are

generally less time-,labor-, and capital-intensive than
other gravimetric methods since they require only a
filtration step.
Electrogravimetry
The deposition as PbO2 at a Pt anode is one example of

electrogravimetry. The reduction of Cu 2+ to Cu at a Pt
cathode is another example of electrogravimetry.
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Summary
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The Language of Analytical Chemistry
Technique: A chemical or physical principle that can

be used to analyze a sample.
Method: A means for analyzing a sample for a
specific analyte in a specific matrix.
Procedure: Written directions outlining how to analyze a
sample
Protocol: A set of written guidelines for analyzing a
sample specified by an agency
Signal: An experimental measurement that is
proportional to the amount of analyte (S).
Calibration The process of ensuring that the signal

measured by a piece of equipment or an instrument
is correct
Standardization The process of establishing the

relationship between the amount of analtye and a
method’s signal.
Validation The process of verifying that a procedure

yields acceptable results.
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Selecting an Analytical Method
Accuracy is a measure of how closely the result of an

experiment agrees with the expected result.
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Precision An indication of the reproducibility of a

measurement or result.
Sensitivity A measure of a method’s ability to

distinguish between two samples; reported as the change in
signal per unit change in the amount of analyte (k).
Detection limit A statistical statement about the smallest

amount of analyte that can be determined with confidence
Selectivity A measure of a method’s freedom from
interferences as defined by the method
Robust: A method that can be applied to analytes

in a wide variety of matrices is considered robust.
Rugged : A method that is insensitive to changes

in experimental conditions is considered rugged.
Method blank: A sample that contains all components

of the matrix except the analyte.
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The
Importance
of Analytical
Methodology
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Introduction Analytical Chemistry-

Equilibrium Constants for Chemical
Reactions
What Is Analytical Chemistry?
“Analytical chemistry is what analytical chemists do.”*
The tools and methods necessary for research

 - for traditional areas of chemistry,
 - fostering multidisciplinary research
 - medicinal chemistry, clinical chemistry, toxicology,
 - Forensic chemistry, material science, geochemistry,
and environmental chemistry.
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The Analytical Perspective
Identify and define the problem.

2. Design the experimental procedure.
3. Conduct an experiment, and gather data.
4. Analyze the experimental data.
5. Propose a solution to the problem
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Discussions pertaining to each of the five steps

outlined in Figure 1.3.
1. What is the analytical problem?

2. What type of information is needed to solve the problem?
3. How will the solution to this problem be used?
4. What criteria were considered in designing the
experimental procedure?
5. Were there any potential interferences that had to be
eliminated? If so, how
were they treated?
Discussions pertaining to each of the five steps outlined

in Figure 1.3.
6. Is there a plan for validating the experimental method?

7. How were the samples collected?
8. Is there evidence that steps 2, 3, and 4 of the analytical
approach are repeated more than once?
9. Was there a successful conclusion to the problem?
3
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Common Analytical Problems
 Qualitative analysis
An analysis in which we determine the
identity of the constituent species in a sample.
 Quantitative analysis
An analysis in which we determine how
much of a constituent species is present
in a samp
Common Analytical Problems
Characterization analysis
An analysis in which we evaluate a
sample’s chemical or physical properties.
Fundamental analysis
An analysis whose purpose is to improve
an analytical method’s capabilities.
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SUMMARY
 Analytical chemists work to improve the ability of all

chemists to make meaningful measurements.
 The need to work with smaller quantities of material,
with more complex materials
 Typical problems on which analytical chemists work
Case study
Read a recent article from the column “Analytical

Approach,” published in Analytical Chemistry, or an
article assigned by your instructor, and write an essay
summarizing the nature of the problem and how it was
solved. As a guide, refer back to Figure 1.3 for one model
of the analytical approach.
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Basic Tools of Analytical Chemistry
SI units: Stands for Système International d’Unités.

These are the internationally agreed on units for
measurements
Scientific notation
A shorthand method for expressing very
large or very small numbers by indicating powers of
ten; for example, 1000 is 1 × 103.
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Significant figures
The digits in a measured quantity,including all digits

known exactly and one digit (the last) whose quantity is
uncertain.
For example, if we weigh a sample on a balance and
record its mass as 1.2637 g,
the sum of 135.621, 0.33, and 21.2163 is 157.17 since
the last digit that is significant for all three numbers is in
the hundredth’s place.
135.621 + 0.33 + 21.2163 = 157.1673 = 157.17
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Significant figures
To the correct number of significant figures using the

following simple rules.
- Retain the least significant figure if it and the digits
that follow are less than halfway to the next higher
digit 12.442 to the nearest tenth gives 12.4
- Increase the least significant figure by 1 if it and the

digits that follow are more than halfway to the next
higher digit 12.476 to the nearest tenth gives 12.5
- If the least significant figure and the digits that follow

are exactly halfway to the next higher digit:
12.550 to the nearest tenth gives 12.6
Basic Equipment and Instrumentation

Balance An apparatus used to measure mass.
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Basic Equipment and Instrumentation
Balances should be placed on heavy

surfaces to minimize the effect of vibrations
in the surrounding environment and should
be maintained in a level position
Equipment for Measuring Volume
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Equipment for Drying Samples
Commercial laboratory ovens are used a muffle furnace used for heating
when the maximum desired samples to maximum temperatures of
temperature is 160–325 °C 1100–1700 °C.
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(a) Desiccator. (b) Desiccator with stopcock for evacuating the desiccator.
Desiccator: A closed container containing a desiccant; used to

store samples in a moisture-free environment.
Desiccant: A drying agent
Equilibrium Chemistry
Reversible Reactions and Chemical Equilibria
In 1798, the chemist Claude Berthollet (1748–1822)
forming NaCl and a precipitate of CaCO3 as products.
equilibrium
A system is at equilibrium
when the concentrations of
reactants and products remain
constant
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Thermodynamics and Equilibrium Chemistry
 The solutes A, B, C, and D, with stoichiometric

coefficients a, b, c, and d.
 Equilibrium constant: For a reaction at equilibrium, the

equilibrium constant determines the relative concentrations
of products and reactant
Manipulating Equilibrium Constants
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Manipulating Equilibrium Constants
Add together two reactions to obtain a new reaction, the

equilibrium constant for the new reaction is the product of
the equilibrium constants for the original reactions.
Example
 Calculate the equilibrium constant for the
reaction, given the following information
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solution
The overall reaction is given as
If Rxn 3 is reversed, giving
then the overall reaction is
and the overall equilibrium constant is
Equilibrium Constants for Chemical Reactions
 Precipitation Reactions
 Precipitate: An insoluble solid that forms when two or
more soluble reagents are combined.
 the reverse reaction describing the dissolution of the

precipitate is more frequently encountered.
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Equilibrium Constants for Chemical Reactions
 The equilibrium constant for this reaction is called

the solubility product, Ksp,
 Solubility product: The equilibrium constant for a

reaction in which a solid dissociates into its ions
(Ksp).
 Remember: Ksp valid only if PbCl2(s) is present and
in equilibrium with the dissolved Pb2+ and Cl–
Acid—Base Reactions
 Brønsted-Lowry definition, acids are proton donors,

and bases are proton acceptors.
 Strong and Weak Acids
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 The equilibrium constant for this reaction is called

an acid dissociation constant, Ka, and is written as
 acid dissociation constant:The equilibrium constant

for a reaction in which an acid donates a proton to
the solvent (Ka).
 Polyprotic acids
Phosphoric acid, has

three acid issociation
reactions and acid
dissociation constants
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Strong and Weak Bases
 strong base is an alkali metal hydroxide
 Weak bases only partially accept protons from the

solvent and are characterized by a base dissociation
constant, Kb.
 Base dissociation constant: The equilibrium constant

for a reaction in which a base accepts a proton from
the solvent (Kb)
Strong and Weak Bases
Amphiprotic Species Some species can behave as either an

acid or a base. For example, the following two reactions show
the chemical reactivity of the bicarbonate ion, HCO3–, in
water.
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The pH Scale
 Dissociation of Water Water is an amphiprotic

solvent in that it can serve as an acid or a base.
 which has a value of 1.0000 × 10–14 at a temperature of

24 °C. The value of Kw varies substantially with
temperature. For example, at 20 °C, Kw is 6.809 × 10–15,
but at 30 °C Kw is 1.469 × 10–14. At the standard state
temperature of 25 °C, Kw is 1.008 × 10–14, which is
sufficiently close to 1.00 × 10–14
The pH Scale
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Example
Tabulating Values for Ka and Kb
The equilibrium constant Kw may

also be expressed as the product of
Ka for CH3COOH and Kb for
CH3COO–. Thus, for a weak acid,
HA, and its conjugate weak base, A–
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Example
Calculate the following equilibrium constants
(a) Kb for pyridine, C5H5N
(b) Kb for dihydrogen phosphate, H2PO4
Solution
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Complexation Reactions
 ligand
A Lewis base that binds with a metal ion.
The following reaction between the metal ion Cd2+
and the ligand NH3 is typical of a complexation
reaction
 Metal–ligand complex
 Formation constant: The equilibrium constant for a

reaction in which a metal and a ligand bind to form a
metal–ligand complex (Kf).
 the reaction between Cd2+ and NH3 involves four

successive reactions
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Oxidation—Reduction Reactions
 Oxidation: A loss of electrons.

 Reduction: A gain of electrons.
Oxidation—Reduction Reactions
Nernst equation: An equation relating electrochemical

potential to the concentrations of products and reactants.
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Example
Calculate (a) the standard-state potential, (b) the equilibrium
constant, and (c) the potential when [Ag+] = 0.020 M and
[Cd2+] = 0.050 M, for the following reaction taking place at
25 °C.
Solution
(a) In this reaction Cd is undergoing oxidation, and Ag+ is
undergoing reduction. The standard-state cell potential,
therefore, is
Solution
b) To calculate the equilibrium constant, the values for the
standard-state potential and number of electrons into
equation
Solving for K gives the equilibrium constant as

log K = 40.6558
K = 4.527 × 1040
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Solution
C). The potential when the [Ag+] is 0.020 M and the
[Cd2+] is 0.050 M is calculated using equation
p-function
A function of the form pX, where
pX = -log(X).
the pH of a solution that is 0.10 M H+ is
 and the pH of 5.0 × 10–13 M H+ is
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Example
What is pNa for a solution of 1.76 × 10–3 M Na3PO4?
SOLUTION
Since each mole of Na3PO4 contains three moles of Na+,
the concentration of
Na+ is
Example
What is the [H+] in a solution that has a pH of 5.16?
SOLUTION
The concentration of H+ is
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Preparing Solutions
Stock solution: A solution of known concentration from

which other solutions are prepared.
Dilution: The process of preparing a less
concentrated solution from a more concentrated
solution.
EX: A laboratory procedure calls for 250 mL of an

approximately 0.10 M solution of NH3. Describe how
you would prepare this solution using a stock solution
of concentrated NH3 (14.8 M).
The Laboratory Notebook
The most important tool when working in the lab,

providing a complete record of all the work
should be able to look back at the laboratory notebook
several years from now and reconstruct the experiments
on worked maner
A laboratory notebook is also a legal document that helps
establish patent rights and proof of discovery
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Problem
1. Indicate how many significant figures are in each of

the following numbers.
a. 903 b. 0.903 c. 1.0903
d. 0.0903 e. 0.09030 f. 9.03 × 102
2. Round each of the following to three significant
figures.
a. 0.89377 b. 0.89328 c. 0.89350
d. 0.8997 e. 0.08907
3. A 250.0-mL aqueous solution contains 45.1 µg of a
pesticide. Express the pesticide’s concentration in
weight percent, parts per million, and parts per billion.
Analysis: A process that provides chemical or physical

information about the constituents in the sample or the
sample itself
Analytes: The constituents of interest in a sample
Matrix: All other constituents in a sample except
for the analytes
Determination: An analysis of a sample to find the
identity, concentration, or properties of the analyte
Measurement: An experimental determination of an
analyte’s chemical or physical propertie
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Techniques, Methods, Procedures, and Protocols
Technique: A chemical or physical principle that can

be used to analyze a sample.
Method: A means for analyzing a sample for a
specific analyte in a specific matrix.
Procedure: Written directions outlining how to
analyze a sample
Protocol:
A set of written guidelines for analyzing
a sample specified by an agency
signal:
An experimental measurement that is
proportional to the amount of analyte (S).
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A method is the application of a technique to a specific

analyte in a specific matrix : design criteria: accuracy,
precision, sensitivity, selectivity, robustness, ruggedness,
scale of operation, analysis time, availability of
equipment, and cost
Accuracy is a measure of how closely the result of an
experiment agrees with the expected result.
Precision An indication of the reproducibility of a

measurement or result.
Sensitivity A measure of a method’s ability to
distinguish between two samples; reported as the change in
signal per unit change in the amount of analyte (k).
Detection limit A statistical statement about the smallest

amount of analyte that can be determined with confidence
Selectivity A measure of a method’s freedom from
interferences as defined by the method
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Robust: A method that can be applied to analytes

in a wide variety of matrices is considered robust.
Rugged : A method that is insensitive to changes
in experimental conditions is considered rugged.
method blank:
A sample that contains all components
of the matrix except the analyte.
Calibration The process of ensuring that the signal
measured by a piece of equipment or an instrument is
correct
standardization The process of establishing the
relationship between the amount of analtye and a
method’s signal.
Validation The process of verifying that a procedure
yields acceptable results.
The
Importance
of Analytical
Methodology
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TITRIMETRIC METHODS

 Stoichiometry refers to the relationship between the quantities

 If a suitable reaction with the analyte does not exist it may be

Figure 2. Example of a thermometric

Figure 3. Additional examples of titration curves.

1. Titrimetric method of analysis is a quantitative

a. The stoichiometry defined, complete reaction, reaction must occur

b. The titrant is air-stable, complete reaction, reaction must occur rapidly,

c. The titrant is air-stable, complete reaction, reaction must occur rapidly,

d. The titrant is air-stable, complete reaction, reaction must occur

5. Which of the following glassware is uesd to measure volume of

6. For accurately determination of the equivalence point, one can

Acid: accepts pair of electron Acid: a proton (H+) donor

Acid: HCl Cl- + H+ HCl/Cl-: acid-conjugate base

Base: NH3 + H+ NH4+ NH3/ NH4 +: base-conjugate acid

NH4+ CH3COOH HCO3- NH3 CH3COO- CO32-

Acid and base could be molecule as well as ion

∙ Water as solvent could be an acid or base

∙ Formamide as solvent could be an acid or base

∙ Alcohol as solvent could be an acid or base

∙ H+ does not exist in a free form

∙ NH4+ + H2O ↔ NH3 + H3O+

2H2O ↔ H3O+ + OH-

[SH] or [H2O]: constant (very few molecules dissociate)

❑ Strong acid: acid that ionizes rapidly and almost completely

Solvent: water or amphoteric protic solvent

∙ A conjugate acid, within the Bronsted–Lowry acid–base theory, is a

∙ Three limitations slowed the development of acid–base titrimetry:

❑ Neutralization is a chemical reaction in which acid and

and its equilibrium constant expression.

∙ The indicator is yellow when the pH is less than pKa – 1

∙ The volume of NaOH needed to reach the equivalence point is

∙ Before the equivalence point, HCl is present in excess and the pH is

∙ After adding 10.0 mL of NaOH the concentration of excess HCl is

∙ The pH at the equivalence point is 7.00.

Step 4: Calculate pH values after the equivalence point by

∙ To find the concentration of H3O+ we use the Kw

∙ To find that the pH is 12.10. Table 1 and Figure 1 show

Figure 3 Titration curve for the

∙ Let’s consider the titration of 50.0 mL of 0.100 M acetic acid, CH3COOH,

and the concentration of acetate is

For example, after adding 10.0 mL of NaOH the concentrations of

∙ Finding that the pH at the equivalence point is 8.79.

Figure 4 Titration curve for the titration of

H2SO4: strong polyprotic acid

❑ Phosphoric acid: three dissociation

pKa1 = 2.1 (H3PO4 H+ + H2PO4-)

pKa2 = 7.2 (H2PO4- H+ + HPO42-)

pKa3= 12.4 (HPO42- H+ + PO43-)

For an amphoteric solvent, SH, the autoprotolysis constant, Ks, relates

∙ The most important limitation imposed by Ks is the change in pH during a

and the pH is 5.3.

and the pOH is 5.3. The titrand’s pH is

∙ In this case the change in pH

Figure 5 Titration curves for 50.0 mL

does not proceed to a significant extent because CH3COO– is a stronger

∙ All other things being equal,

and the net reaction between CO2 and OH– is

Under these conditions some OH– is consumed in neutralizing CO2,

When preparing a solution of NaOH, be sure to use water that is free

Acid–base titrimetry is a standard method for the quantitative

Boric acid’s Ka value increases to 1.5 × 10–4 in the presence of

The NH3 is removed by distillation and titrated with HCl.