Analytical Chemistry – Finals Reviewer of Khyd indicates that the concentration of CO2(aq) is

(Modules, Skoog, Other Books) much larger than the concentration of H2CO3 (that is,
Galendez, Cristian Rey M. [H2CO3] is only about 0.3% that of [CO2(aq)]).
BSES – 2NRM1 Thus, a more useful way of discussing the acidity of
A.Y. 2023-24 solutions of carbon dioxide is to combine Equation
15-3 and 15-4 to give
Chapter 1 : Titration Curves for Polyfunctional
Acids and Bases

• Polyfunctional Acids and Bases

- contains 2 or 3 acidic or basic groups which

normally differ in strength and as a consequence,
exhibit two or more end points in neutralization
titration
- several species of interest in analytical chemistry
that have two or more acidic or basic functional • Sample Problem/s
groups.
Ex.1
• The Phosphoric Acid System

- Phosphoric acid is a typical polyfunctional acid.

In aqueous solution, it undergoes the following
three dissociation reactions:

Note:
- Throughout the remainder of this chapter, we use
Ka1, Ka2 to represent the first and second
dissociation constants of acids and Kb1, Kb2 to
represent the stepwise constants of bases.

- Generally, Ka1 . Ka2, often by a factor of 10^4 to

10^5 because of electrostatic forces. That is, the
first dissociation involves separating a single
positively charged hydronium ion from a singly
charged anion. In the second step, the hydronium
ion must be separated from a doubly charged
anion, a process that requires considerably more
energy.

• The Carbon Dioxide/Carbonic Acid

System

- When carbon dioxide is dissolved in water, a

dibasic acid system is formed by the following
reactions:

- The first reaction describes the hydration of aqueous

CO2 to form carbonic acid. Note that the magnitude
Chapter 2 Titration Curves for Polyfunctional Acids
and Bases

• Titration Curves for Polyfunctional Acids

- Compounds with two or more acidic functional

groups yield multiple end points in a titration if
the functional groups differ sufficiently in
strength as acids.

EQN. 3

• Titration Curve for Polyfunctional Bases

- The same principles just described for

constructing titration curves for polyfunctional
acids can be applied to titration curves for
polyfunctional bases
 Sample Problem/s

Ex1.
Chapter 3 Precipitation Titrimetry

• Precipitation Titrimetry

- Precipitation titrations are based on reactions that

yield ionic compounds of limited solubility.
- one of the oldest analytical techniques (mid-80’s).
- The slow rate at which most precipitates form,
however, limits the number of precipitating
agents that can be used in titrations to a handful.
- type of titration which involves the formation of
precipitate. II. The Fajans Method
- the titrant reacts with the analyte and forms an
insoluble substance called a precipitate. - A.K.A. indicator adsorption (on the surface)
- continues till the last amount of analyte is method
consumed. It is used to determine chloride by - Described by Kazimierz Fajans
using silver ions. - Indicator: Dichlorofluorescein
- End Point: Green
- Titrations involving adsorption indicators are
• Argentometric Titrations rapid, accurate, and reliable, but their application
is limited to the few precipitation titrations that
- Titrations with silver nitrate. form colloidal precipitates rapidly.
- Silver is Ag which is taken from its Latin name - an organic compound that adsorbs onto or
Argentum. desorbs from the surface of the solid in a
precipitation titration. Ideally, the adsorption or
• Methods of Argentometric Titration desorption occurs near the equivalence point and
results not only in a color change but also in the
I. The Volhard Method transfer of color from the solution to the solid or
vice versa.
- A.K.A. Indirect Back Tritation
- Described by Jacob Volhard, German Chemist in Steps/Procedure
1874
- Indicator: Iron (III) - Before the equivalence point:
- End Point: Red o The surface of the precipitant particles
- The Volhard method is one of the most common will be negatively charged due to the
argentometric methods. In this method, silver adsorption of excess Cl. the surface of the
ions are titrated with a standard solution of particles.
thiocyanate ion: o The anionic (fluoresceinate) indicator is
repelled.
o A diffuse positive counter-ion layer will
surround the particles.
- The solution turns red with the first slight excess - At equivalence point:
of thiocyanate ion due to the formation of o There is no longer an excess of analyte
Fe(SCN)2+. The most important application is the Cl- , and the surface of the colloidal
indirect determination of halide ions. particles are largely neutral.
- The titration is performed only in acidic medium - After the equivalence point:
(HNO3) to prevent precipitation of iron o There will be an excess of titrant Ag+
hydroxides, Fe(OH)3 . adsorb to the AgCl precipitates.
o The negatively charged fluoresceinate
reacts to the excess Ag+ ions at the
surface of AgCl precipitates producing a
Steps/Procedure
reddish-colored surface.
- Analyte is treated with the measured excess of
Silver Nitrate:

X + Ag+ -> AgX + Ag+(residual/excess)

- The unreacted silver ions Ag+(Excess) are

titrated with standard solution of Thiocyanate
III. The Mohr Method
ion, using Fe(III) as indicator:
- Indicator: sodium chromate
Ag+(excess) + SCN- -> AgSCN
- End-Point: Brick Red
- Silver ions react with chromate to form the brick-
- The first slight excess of Thiocyanate ion gives
red silver chromate (Ag2CrO4) precipitate in the
red color of FeSCN2+:
equivalence-point region.
Fe3+ + SCN- -> FeSCN2+
 Steps/Procedure

- before the addition of any silver nitrate the

chromate indicator gives the clear solution a
lemon-yellow color. Gradual addition of silver
solution,white precipitate of silver chloride
forms:

- At the endpoint, all the Cl- ions have precipitated.

The slightest excess of Ag+ precipitates with the
chromate indicator giving a slight red-brown
colouration:

- If addition of Ag+ continued past the endpoint, Sample Problem/s

more silver chromate is formed which appears as
a stronger red-brown colour. Ex.1
Perform calculations needed to generate a titration curve
***This method should be carried out under conditions of for 50.0 mL of 0.0500 M NaCl with 0.1000 M AgNO3
pH 6.5 – 9.0 to prevent: (for AgCl, Ksp = 1.82 x 10-10).

- precipitation of silver hydroxide formation at pH

> 10: Solution:

- p[Ag] at Initial Point:

Use Ksp to get [Ag+]. That is
- removal by an acid-base reaction to form

p[Ag] = -log( )= 8.44

hydrogen chromate ions or dichromate ion at pH
< 7:

- p[Ag] at Pre=equivalence point: After the

addition of 10.0 mL AgNO3

o Titrate using normal Titration (Pre-)

*** At this condition, the [CrO4 2− ] become lower which
requires more Ag+ to be added to reach end point and
cause error. o Find p[Ag] (Pre-)

p[Ag] = -log( )= 8.14

- p[Ag] at Equivalence point: After the addition of
25.0 mL pf AgNO3

- p[Ag] at Post-Equivalence point: After the

addition of 26.0 mL of AgNO3

o Titrate using normal Titration (Post-)

=1.316 x 10-3M

o Find p[Ag] (Post-)

p[Ag] = -log(1.316 x 10-3)= 2.88
Chapter 4 Complexometric Titrations (P443)
- A volumetric titration involves the formation of
soluble complex between metal ion (as acceptor)
and ligand (as donor) to form coordination bonds.

- The donor species, or ligand, must have at least

one pair of unshared electrons available for bond • Nature of The Donor Atom
formation. Water, ammonia, and halide ions are - In aqueous solution, donors are nonmetallic
common inorganic ligands. elements N, O, and S.
- A ligand is an ion or a molecule that forms a
covalent bond with a cation or a neutral metal
atom by donating a pair of electrons, which are
then shared by the two.
- Complex Ion = Transition Metal Cation
Surrounded by Ligands.
- The metallic ion (atom) has stable electronic
configuration It forms additional completed
shells by accepting electron pairs from donor
atoms.
- Coordination number/Bonding is the number
of covalent bonds that a cation tends to form with
electron donors. It could be 2, 4, 6, depending on
the metal ion and its oxidation number and is Types of complexing agents (ligands)
independent on the nature of donor atom.
1. Unidentate (Monodentate) Ligand/Simple
Examples: Ligand
- The ligand attached to metal at one site e.g. H2O,
= 4 bonding NH3, CN-, Cl-, I-, Br- (i.e. forming one
coordinate bond, or capable of donating one
unshared pair of electrons)
= 6 bonds

Application/s

- You are an analyst at a company for water 2. Bidentate Ligand

purification, and you need to estimate the water - The ligand attached to metal at two sites
hardness (Ca2+ & Mg2+ amount)
Your Job: Plan and design the chemical analysis approach
to perform this task.

• Complex (Coordination Compound) 3. Tridentate Ligands

- Compound results from the combination of metal - The ligand attached to metal at 3 sites
ion as (acceptor) with donor molecules (ligand)
through coordinated bonds (donor→ acceptor)

Lewis Acid Lewis Base

4. Tetradentate Ligands
Metal Ion (Ag+) + Ligand (NH3) → COMPLEX
- The ligand attached to metal at 4 sites
(Coordination Compound)

Example: [Ag(NH3)2]+

5. Multidentate Ligands (Chelating Agent)

- Substance with multiple sites available for
coordination bonding with metal ions. Such
bonding typically results in the formation of five
or six membered rings
 Ethylene Diamine Tetra acetic Acid 2. Nature of the Metal Ion
• Complexes of divalent cations: only stable in
basic medium
• Chelates of trivalent cations: stable in acidic
media (pH 1-2).
• Chelates of tetravalent cations: stable at pH
values less than 1.

Stability constants for some metal-EDTA chelates

CHELATION

- Chelate: A complex formed between the ligand

containing two or more donor atoms and a metal,
forming ring structure (heterocyclic rings or
chelate rings).
- Chelating agents: organic molecules containing
two or more donor groups that combine with
metal to form a complex of ring structure.

- Chelate effect: Enhancing the stability of

multidentate complexes than unidentate
complexes.

Titration With Multidentate Complexers (Chelating

Agents

- Chelating agent: Ethylene diamine tetra acetic

acid (EDTA) possess enough donor atoms to fill
the whole coordination sphere of metal ions in
one step.

The three-dimensional structure of the 1:1 metal-EDTA

chelate with Mn2+.

Factors Affecting the Stability of Metal-EDTA

Chelate

Where:
- Y is EDTA

1. pH of the solution
 Sample Problem/s Part b. Find [MgY2-]

Ex1. Consider the titration of 50.0 mL of 0.1 M solution

of Mg2+ (buffered at pH 10) with 0.1 M EDTA solution.

Solution: Part C. Find x using Kstab

I. Initial Point

𝑀𝑔2+ = 0.1, so, pMg = -log(o.1) = 1.0

5
( )
II. Pre-equivalence Point: Addition of 10.0 = (𝑥)(1/110) = 5.0 × 108 = 𝑥 = 1 × 10−8M
110

mL EDTA
(𝑇𝑖𝑡𝑟𝑎𝑛𝑑⁡𝑉 ∗ 𝑚𝑜𝑙) − (𝑇𝑖𝑡𝑟𝑎𝑛𝑡⁡𝑉 ∗ 𝑚𝑜𝑙)
𝑝𝑀𝑔 = −log⁡(⁡ ) Part D. find pMG
𝑇𝑜𝑡𝑎𝑙⁡𝑣𝑜𝑙𝑢𝑚𝑒
(50𝑚𝐿 ∗ 0.1𝑀) − (10.0𝑚𝐿 ∗ 0.1𝑀)
𝑝𝑀𝑔 = −log⁡(⁡ ) pMG = -log(x) = -log(1.0 x 10-8 M) = 8.0
50 + 10
𝑝𝑀𝑔 = 1.17
Note:
- Pre-equivalence point may occur as many as
possible before reaching equivalence point. In
this example, only 1 pre-equivalence point was
shown. Moreover, all pre-equivalence points
have the same solution.

III. Equivalence Point

- At this Point, 50 mL of EDTA have been added to
completely react with Mg solution

Part a. Do the ICE method

Mg2+ Y4- MgY2-

x x F–x

Part B. Use the given Kstab and substitute

𝐹−𝑥
= = 5.0 × 108
(𝑥)(𝑥)
𝐹−𝑥 8
= = 5.0 × 10
𝑥2
- at this point, solve for x using shift-solve.

Kstab = 9.9 x 10-6 = 1.0 x 10-5 M

Part C. Solve for pMG using the value of Kstab

pMG = -log(Kstab) = -log(1.0 x 10-5 M) = 5.0

IV. Post-equivalence point: Addition of 60mL

of the 0.1 M EDTA

- In this point, find the excess of EDTA solution

and the amount of Complex (MgY2-)

Part a. Find [EDTA] or [Y4-]

 Characteristics of Metal Ion Indicators

I. Form colored chelates (complexes) and

exhibit a different color in the free form than
in the complex form.
II. The reaction between metal and indicator
must be reversible.
III. The metal-indicator complex should be less
stable than the metal-EDTA complex.
IV. The color reaction should be specific or at
least selective.
V. Changes its color according to the pH of the
medium.

Examples of Metal Ion Indicators

1. Eriochrome black T (EBT)

- It can be represented by H2In-. The color of

Indicator changes with the change of pH. EBT
contains 2 replaceable phenolic hydrogen.
-
TYPES OF COMPLEXOMETRIC TITRATIONS

1. Direct Titration

- The solution of the metal ion to be determined is

buffered to the desired pH( e.g. to pH=10 with
- EBT is a tribasic acid at pH 10, exists as blue
NH4+, NH4OH) and titrated directly with the
HIn2-
standard EDTA solution.
- The end point is determined by the change in
color of a metal indicator that responds to changes
in pM.
- The blue form of the indicator reacts with metal
ions, to give a wine red chelate

Requirements for Direct EDTA Titrations

- By the titration with EDTA, it initially chelates
the free Mg2+ ion, then displaces the chelated Mg I. M-EDTA complex must be more stable than
from the indicator. M-Ind. complex in buffered medium.
II. The compound to be determined is water
soluble
III. The reaction between EDTA and metal must
- EBT is used for the determination of Mg 2+, Zn be rapid. If not, it must be catalyzed.
2+, Cd 2+, pb 2+, Hg 2+ & Mn 2+ salt at pH 7 – IV. Mn+ should not be precipitated at the pH of
11 using ammonia buffer (pH = 10) titration. If Mn+ is precipitated as MOH,
- EBT cannot be used for the determination of Cu auxiliary reagent must be added to prevent
2+, Fe 3+, Al 3+, Co 2+ and Ni 2+ pptn. of Mn+

2. Murexide Direct Determination of Water Hardness

- Ammonium salt of purpuric acid and its anion has • Water hardness is due to the presence of Ca2+ &
the following structure Mg2+ salts.
• EDTA forms complex with Ca2+ & Mg2+
• Ca-EDTA complex is more stable than Mg-EDTA
complex.
• Murexide is used for the direct titration of
• At pH 12 EDTA forms complex with Ca2+ only.
calcium at pH=12, the end point changes from red
to blue violet.
2. Back Titration
• At pH=12, Mg-murexide is less stable than the
Ca-complex, so Ca2+ ion can be titrated in the
- Addition of known excess of standard EDTA
presence of Mg at this pH.
solution to the sample
• Murexide gives yellow chelates with Cu, Co, Ni
- The medium is buffered.
metals ions.
- Titrate excess EDTA with standard metal ion
solution such as Mg2+ or Zn2+
- The color change at the end point
 Chapter 5 Equilibrium Calculations Involving EDTA EDTA TITRATIO CURVE

- EDTA titrations are always performed in

solutions that are buffered to a known pH to avoid
interferences by other cations or to ensure
satisfactory indicator behavior.

- Region 1: Excess Mn+ left after each addition of

EDTA. Conc. of free metal equal to conc. of
unreacted Mn+.
COMMULATIVE STABILITY CONSTANT
- Region 2: Equivalence point: [Mn+ ] = [EDTA]
Some free Mn+ generated by MYn-4  Mn+ +
EDTA
- Region 3:Excess EDTA. Virtually all metal in
MYn-4 form.

- Since EDTA is a tetraprotic acid, the stepwise

dissociation of EDTA as follows :

Y4- form of EDTA is the predominate form at pH greater

than 10.

Conditional Formation Constant K’MY

• It can be used to calculate the equilibrium

concentration of the metal ion and the complex at
the equivalence point and where there is an excess
of reactant.
• Using CEDTA instead of Y4- in
determination of K’MY simplifies calculations
 Sample Problem/s

Ex.1. Calculate pCa in 100 ml of a solution of 0.100 M

Ca2+ at pH10 after addition of 0, 50, 100, 150 ml of 0.100
M EDTA. Kf for CaY2- is 5.0x1010 and α4 is 0.35.
𝑥 = 1.14 × 10−10M
Sol’n.
Part D. find pMG
I. Initial Point
pMG = -log(x) = -log(1.14 x 10-10 M) = 9.94

Ex.2. A primary-standard zinc metal ion solution was

prepared by dissolving 0.2619 g of primary-standard-
II. Addition of 0.00 ml EDTA grade zinc metal in dilute HCl and adding distilled water
to the mark in a 250 mL (0.2500 L) volumetric flask. Zn
MW = 65.37 g / mol. Calculate the molarity of the zinc
metal ions in the solution. State the value to 5 places after
the decimal point.
III. Addition of 50 mL EDTA: Pre-
Equivalence Solution:
(𝑇𝑖𝑡𝑟𝑎𝑛𝑑⁡𝑉 ∗ 𝑚𝑜𝑙) − (𝑇𝑖𝑡𝑟𝑎𝑛𝑡⁡𝑉 − 𝑚𝑜𝑙)
𝑝𝐶𝑎 = −log⁡(⁡ )
𝑇𝑜𝑡𝑎𝑙⁡𝑣𝑜𝑙𝑢𝑚𝑒
(100𝑚𝐿 ∗ 0.1⁡𝑀) − (50𝑚𝐿 ∗ 0.1⁡𝑀)
𝑝𝐶𝑎 = −log⁡(⁡ )
100 + 50

𝒑𝑪𝒂 = 𝟏. 𝟒𝟖

IV. Addition of 100 mL EDTA: Equivalence Ex.3. An EDTA solution of unknown molarity was
standardized by titration of 10.00 mL (0.01000 L) samples
Part a. find [EDTA] of the standard zinc ion solution of Example 1 by the
method of this experiment. The mean corrected titration
volume of the EDTA solution was 16.25 mL (0.01625 L).
Part b. Find [Ca2+] + [Y4-+] The reaction between EDTA and all metal ions is 1 mol to
Ca2+ Y4- CaY2- 1 mol. Calculate the molarity of the EDTA solution. State
x x 0.05 the value to 5 places after the decimal point.

[𝐶𝑎𝑌2−]
𝐾𝑠𝑡𝑎𝑏 = = 5.0 × 108
[𝐶𝑎][𝐸𝐷𝑇𝐴]
[𝐶𝑎𝑌2−]
= 1.75 × 1010
[𝐶𝑎][𝐸𝐷𝑇𝐴]
0.05
2
= 1.75 × 1010 Ex.4. A zinc supplement tablet containing (nominally)
𝑥 about 10 mg of zinc ion was added to water and titrated
𝑥 = 1.69⁡ × 10−6 with 0.01000 M (= 0.01000 mmol / mL) EDTA solution
Part c. find pCa by the method of this experiment. The corrected titration
volume of the EDTA solution was 14.65 mL. Calculate
the zinc content of the tablet in mg units. State the value
to 2 places after the decimal point.

V. Addition of 150 mL EDTA: Post-

equivalence

Part a. Find [CaY2-]

Part b. Find [EDTA] or [Y4-]

Part C. Find x using Kstab