TITRATION

Group 6 – Circinus

Quick Refresh!
(Note: What are discussed below until the rule of thumb are recaps that we can use for acid-
base titrations.)
Before we start discussing about titration and titration curves, we should quickly refresh the
concept of a weak/strong acid and weak/strong base.
A strong acid dissociates (or ionizes) completely in aqueous solution to form hydronium ions
(H3O+).
HCl + H2O H3O+ + Cl-
A weak acid does not dissociate completely in aqueous solution to form hydronium ions (H 3O+).
CH3COOH + H2O CH3COOH + H3O+ + CH3COO-
A strong base dissociates completely in aqueous solution to form hydroxide ions (OH -).
NaOH + H2O N+ + OH-
A weak base does not dissociate completely in aqueous solution to form hydroxide ions (OH -).
NH4OH + H2O NH4OH + NH4+ + OH-

Type Examples

Strong Acids hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric acid (HNO3)

Weak Acids acetic acid (CH3COOH), hydrofluoric acid (HF), oxalic acid (COOH)2

sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide

Strong Bases
(LiOH)

Weak Bases ammonium hydroxide (NH4OH), ammonia (NH3)

Weak acids and weak bases always exist as conjugate acid-base pairs in an aqueous solution as
represented below
 HA + H2O H3O+ + A-
Here, HA is the acid and A- is termed as the conjugate base of HA. H2O is the base and its
conjugate acid is H3O+.
A- + H2O OH- + HA
In the above reaction, A- is a base and HA is the conjugate acid of A-. H2O is the acid and its
conjugate base is OH-.

Rule of Thumb
Weak acids have strong conjugate bases, while weak bases have strong conjugate acids.
As shown in the above two reactions, if HA is a weak acid, then its conjugate base A - will be a
strong base. Similarly, if A- is a weak base, then its conjugate acid HA will be a strong acid.

How do we define titration?

Titration is a technique to determine the concentration of an unknown solution.
Titrant
It is the solution of a known concentration, which is added to another solution whose
concentration has to be determined.
Analyte or Titrand
It is the solution whose concentration has to be determined.
Equivalence Point
It is the point in titration at which the amount of titrant added is just enough to completely
neutralize the analyte solution.
At the equivalence point in an acid-base titration, moles of base = moles of acid and the solution
only contains salt and water.
Indicator
An indicator is a weak acid or base that is added to the analyte solution, and it changes
color when the equivalence point is reached.
Endpoint
It refers to the point at which the indicator changes color in an acid-base titration.
Equivalence Point vs. Endpoint
Though the terms equivalence point and endpoint are often used interchangeably, they are
different terms. Equivalence point is the theoretical completion of the reaction: the volume of
added titrant at which the number of moles of titrant is equal to the number of moles of
analyte.
Endpoint is what is actually measured, a physical change in the solution as determined by
an indicator or an instrument mentioned above.
There is a slight difference between the endpoint and the equivalence point of the titration.
This error is referred to as an indicator error, and it is indeterminate.
Equivalence point comes before the end point.
To get the same equivalent point as the end point, pH of the indicator should match the pH at
the equivalence.
pHindicator = pHat equivalent point
The equivalence point is the exact point in a titration when moles of one titrant equal the moles
of the substance being titrated. The endpoint is the point where the system changes when the
moles of the reacting titrant exceed the moles of the substance being titrated. This can be seen
as a sharp change in pH, a surge of voltage, a change in the color of the indicator, etc. the
difference between the equivalence point and the endpoint is an indeterminate error in all
titrations.

As illustrated in the titration setup at the left, a

solution of known concentration (titrant) is used to
determine the concentration of an unknown solution
(titrand or analyte).
Typically, the titrant (the solution of known
concentration) is added through a burette to a known
volume of the analyte (the solution of unknown
concentration) until the reaction is complete. Knowing
the volume of titrant added allows us to determine
the concentration of the unknown analyte. Often,
an indicator is used to signal the end of the reaction,
the endpoint. Titrant and analyte is a pair of acid and
base. Acid-base titrations are monitored by the change
of pH as titration progresses.
More explanations:
A typical titration begins with a beaker or Erlenmeyer flask containing a very precise volume of
the analyte and a small amount of indicator (such as phenolphthalein) placed underneath a
calibrated burette or chemistry pipetting syringe containing the titrant. Small volumes of the
titrant are then added to the analyte and indicator until the indicator changes color in reaction
to the titrant saturation threshold, representing arrival at the endpoint of the titration.
Depending on the endpoint desired, single drops or less than a single drop of the titrant can
make the difference between a permanent and temporary change in the indicator. When the
endpoint of the reaction is reached, the volume of reactant consumed is measured and used to
calculate the concentration of analyte by
Ct V t X
C a=
Va

where Ca is the concentration of the analyte, typically in molarity; Ct is the concentration of the
titrant, typically in molarity; Vt is the volume of the titrant used, typically in liters; X is the mole
ratio of the analyte and reactant from the balanced chemical equation; and Va is the volume of
the analyte used, typically in liters.

What is a titration curve?

A titration curve is the plot of the pH of the analyte solution versus the volume of the titrant
added as the titration progresses.

Titration of a Strong Acid with a Strong Base

Suppose our analyte is hydrochloric acid HCl (strong acid) and the titrant is sodium hydroxide
NaOH (strong base). If we start plotting the pH of the analyte against the volume of NaOH that
we are adding from the burette, we will get a titration curve as shown below.
 HCl + H2O H3O+ + Cl-
Point 1: No NaOH added yet, so the pH of the analyte is low (it predominantly contains
H3O+ from dissociation of HCl).
As NaOH is added dropwise, H3O+ produced by dissociation of NaOH. Analyte is still acidic
due to predominance of H3O+ ions.
Point 2: This is the pH recorded at a time point just before complete neutralization takes
place.
Point 3: This is the equivalence point (halfway up the steep curve). At this point, moles of
NaOH added = moles of HCl in the analyte. At this point, H3O+ ions are completely
neutralized by OH- ions. The solution only has salt (NaCl) and water and therefore the pH is
neutral i.e. pH = 7.
at equivalence point
HCl + NaOH NaCl + H2O
Point 4: Addition of NaOH continues, pH starts becoming basic because HCl has been
completely neutralized and now excess of OH- ions are present in the solution (from
dissociation of NaOH).
after equivalence point
NaOH Na+ + OH-

Titration of a Weak Acid with a Weak Base

Suppose our analyte is NH3 (weak base) and the titrant is acetic acid CH3COOH (weak acid). If
we start plotting the pH of the analyte against the volume of acetic acid that we are adding
from the burette, we will get a titration curve as shown below.
If you notice there isn’t any steep bit in this plot. There is just what we call a ‘point of inflexion’
at the equivalence point. Lack of any steep change in pH throughout the titration renders
titration of a weak base versus a weak acid difficult, and not much information can be extracted
from such a curve.

What to do when you encounter normality problems?

When you complete a titration, you will have three pieces of data: the volumes of the acid
solution and the base solution required to reach the endpoint and the concentration of one of
those two solutions.

MA or NA acid concentration

MB or NB base concentration

VA volume of the acid

VB volume of the base

at the endpoint
equivalents of acid = equivalents of base
NAVA = NBVB
The calculations are easiest when you use normality for the concentration, because
normality is based on equivalents and one equivalent of any acid exactly neutralizes one
 equivalent of any base.  Therefore, at the endpoint, the number of equivalents of acid must
be the same as the number of equivalents of base.
Recall that an equivalent is the amount of acid (or base) that delivers one mole of H + (or
OH-) ions.  If the number of equivalents of acid is the same as the number of equivalents of
base, then the number of H+ ions must be the same as the number of OH- ions, and the two
will just exactly neutralize each other.

Problems!
1. If 25.00 mL of citric acid solution is titrated with 28.12 mL of 0.1718 N KOH, what is the
concentration of citric acid? 
H3AsO4 + 2NaOH Na2HAsO4 + 2H2O
NAVA = NBVB
NBVB
NA ¿
VA
(0.1718 N KOH)(28.12mL KOH )
NA¿
25.00 mL C 6 H 8 O 7
NA = 0.1932 N
Therefore, normality of the citric acid is 0.1932 N.
2. For example an unknown molarity of HCl acts as the analyte. 50 mL of it is placed into a
flask and a 0.1 M solution of NaOH will be the reagent. The endpoint is pH=7 so
litmus, with a pKa of 6.5 is chosen. The color of the solution changes when 10 mL of 0.1
M NaOH is added.
HCl(aq) + NaOH(aq) H2O(l) + OH- (aq) + Cl-
Or just the net ionic equation

H+ + OH- H2O(l)
M NaOH V NaOH X
M HCl =
V HCl

M HCl =
( 0.1 M NaOH ) (10 mL NaOH ) ( 10001 LmL ) (1 mol NaOH )
1L
50 mL HCl (
1000 mL )
¿¿

¿ 0.020 M HCl

¿ 2 x 10−2 M HCl
Types of Titrations
1. Acid-Base Titrations
A way of determining acid or base concentration in a solution. Acid-Base titrations are
usually used to find the amount of a known acidic or basic substance through acid base
reactions. The analyte (titrand) is the solution with an unknown molarity. The reagent
(titrant) is the solution with a known molarity that will react with the analyte.
Example
Titration reveals that 11.6 mL of 3.0 M sulfuric acid are required to neutralize the
sodium hydroxide in 25.00 mL of NaOH solution. What is the molarity of the NaOH
solution?

Given: Vacid = 11.6 mL H2SO4

Macid = 3.0 M
Vbase = 25.00 mL NaOH
Unknown: Mbase
Step 1: Convert mL to L
1L
11.6 mL H2SO4 ( ) = 0.0116 L H2SO4
1000 mL
1L
25.00 mL NaOH ( ) = 0.025 L NaOH
1000 mL
Step 2: Find the moles of titrant
nacid
Macid =
L
nacid
3.0 M H2SO4 =
0.0116 L
nacid = 3.0 M H2SO4 (0.0116 L H2SO4)
= 0.0348 mol H2SO4
Step 3: Apply mole ratio
 2  mol   NaOH
0.0348 mol H2SO4 ( ) = 0.0696 NaOH
1  mol  H2 SO 4
Step 4: Find the molarity of the analyte
mol
Mbase =
L
0.0696 mol NaOH
=
0.025 L NaOH
= 2.784
= 2.8 M NaOH

2. Gas Phase Titrations

Gas phase titrations are titrations done in the gas phase, specifically as methods for
determining reactive species by reaction with an excess of some other gas, acting as the titrant.
Example
In a chemiluminescence procedure, a NO2 analyzer is calibrated by the gas phase titration of NO
with O3 that produces NO2 stoichiometrically.
O3 + NO O2 + NO2
If a sample of 40.0 mL of O3 was titrated with 20.0 mL of 0.89 N NO, what is the concentration
of the analyte?
NAVA = NBVB
NBVB
NA ¿
VA
(0.89 N NO )(20.0 mL NO)
NA¿
40.00 mLC 3
NA = 0.445 N NO

3. Precipitation Titration
A reaction in which the analyte and titrant form an insoluble precipitate also can serve as the
basis for a titration.
THREE GENERAL TYPES OF INDICATORS FOR PRECIPITATION TITRATIONS
a. MOHR METHOD
The first type of indicator is a species that forms a precipitate with the titrant. The Mohr
method was first published in 1855 by Karl Friedrich Mohr. 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.
b. VOLHARD METHOD
A second type of indicator uses a species that forms a colored complex with the titrant or the
titrand. The Volhard method was first published in 1874 by Jacob Volhard. 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 must be carried out in an acidic solution to prevent the
precipitation of Fe3+ as Fe(OH)3.
c. FAJANS METHOD
The third type of end point uses a species that changes color when it adsorbs to the precipitate.
The Fajans method was first published in the 1920s by Kasimir Fajans. 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.

4. Redox Titration

Redox titrations are based on a reduction-oxidation reaction between an oxidizing agent and a

reducing agent.
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 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.
A potentiometer or a redox indicator is usually used to determine the endpoint of the titration,
as when one of the constituents is the oxidizing agent potassium dichromate.
 The color change of the solution from orange to green is not definite, therefore an indicator
such as sodium diphenylamine is used.[29] Analysis of wines for sulfur dioxide requires iodine as
an oxidizing agent. In this case, starch is used as an indicator; a blue starch-iodine complex is
formed in the presence of excess iodine, signalling the endpoint.
Some redox titrations do not require an indicator, due to the intense color of the constituents.
For instance, in permanganometry a slight persisting pink color signals the endpoint of the
titration because of the color of the excess oxidizing agent potassium
permanganate. In iodometry, at sufficiently large concentrations, the disappearance of the
deep red-brown triiodide ion can itself be used as an endpoint, though at lower concentrations
sensitivity is improved by adding starch indicator, which forms an intensely blue complex with
triiodide.
Redox Titration Curves
to monitor the titration reaction’s potential instead of the concentration of one species.

Ared + Box ⇌ Bred + Aox

Consider, for example, a titration in which a titrand in a reduced state, Ared, reacts with a titrant
in an oxidized state, Box. where Aox is the titrand’s oxidized form, and Bred is the titrant’s reduced
form.
Erxn = EBox/Bred – EAox/Ared

where Aox is the titrand’s oxidized form, and Bred is the titrant’s reduced form. The reaction’s
potential, Erxn, is the difference between the reduction potentials for each half-reaction.
EBox/Bred = EAox/Ared
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 because we can use either half-reaction to monitor the
titration’s progress.
RT [ Ared]
Erxn =E Aox / Ared −¿ ln
nF [ Aox ]
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
 RT [Bred ]
Erxn =EBox / Bred −¿ ln
nF [Box ]
After the equivalence point it is easier to calculate the potential using the Nernst equation for
the titrant’s half-reaction.

5. Complexometric Titration
It is a form of volumetric analysis in which the formation of a colored complex is used to
indicate the end point of a titration.
Ethylenediaminetetraacetic acid, or EDTA, is an aminocarboxylic acid. EDTA, which is shown in
the figure below in its fully deprotonated form, is a Lewis acid with six binding sites—four
negatively charged carboxylate groups and two tertiary amino groups—that can donate 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 9.26b), 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. Ethylenediaminetetraacetic acid, or EDTA, is an aminocarboxylic acid.
EDTA, which is shown in Figure 9.26a in its fully deprotonated form, is a Lewis acid with six
binding sites—four negatively charged carboxylate groups and two tertiary amino groups—that
can donate 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 9.26b), 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 1.2 Structures of (a) EDTA, in its fully deprotonated form, and (b) in a six-coordinate
metal–EDTA complex with a divalent metal ion.
Example
The concentration of a solution of EDTA was determined by standardizing against a solution of
Ca2+ prepared using a primary standard of CaCO3. A 0.4071-g sample of CaCO3 was 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 was
adjusted by adding 5 mL of a pH 10 NH3–NH4Cl buffer containing a small amount of Mg2+–EDTA.
After adding calmagite as an indicator, the solution was titrated with the EDTA, requiring 42.63
mL to reach the end point. Report the molar concentration of EDTA in the titrant.
The primary standard of Ca2+ has a concentration of

0.4071 g CaCO 3
M =D ( MW )= ( 0.5000 LCaCO 3 )
¿

The moles of Ca2+ in the titrand is

n = MV
= (8.135×10−3 M Ca2+)(0.05000 L Ca2+)
=4.068×10-4 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
MEDTA = nEDTA / VEDTA
4.068×10 -4  mol  EDTA
= 0.04263 L EDTA

=9 .543×10−3 M EDTA

References:
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Book
%3A_Analytical_Chemistry_2.0_(Harvey)/09_Titrimetric_Methods/9.2%3A_Acid
%E2%80%93Base_Titrations?
fbclid=IwAR19Ijx4LTFmPW1Rixh4RiIioOIEbsuflzidTx2f6ZoyAfL2CseGqNal_90

https://www.khanacademy.org/test-prep/mcat/chemical-processes/titrations-and-solubility-
equilibria/a/acid-base-titration-curves?fbclid=IwAR1AD1AQ-3W-
3qEOZYio41PxO5nAEZGjIIM5NrkqLr5uej5x62we8ExQKIU

http://dl.clackamas.edu/ch105/lesson6titration_calculations.html?
fbclid=IwAR3fDaV2tcaY6wl0uF9zlL0ny9Bmxmz4dnDq-5jacAt3d-CJDm_LoBu5nTw

https://preparatorychemistry.com/Bishop_Titration.htm
http://spots.gru.edu/smyers1/Chemistry2810/Homework/NormalitySolutions.htm

https://byjus.com/jee/normality/