Titrimetric

Methods

Titrations
- widely used in analytical chemistry to determine acids,
bases, oxidants, reductants, metal ions, proteins, and
many other species.
Titration methods (titrimetric methods)
-include a large and powerful group of quantitative
procedures based on measuring the amount of a reagent
of known concentration that is consumed by an analyte
in a chemical or electrochemical reaction.
- concentration of the unknown can be calculated using
the stoichiometry of the reaction and the number of
moles of standard solution required to reach the end
point

Titrimetric methods
-Widely used for routine determination because they are rapid, convenient,
accurate, and readily automated
Types
Volumetric Titrimetry
-Involves measuring the the volume of a solution of known concentration that
is required to react essentially completely with the analyte
Gravimetric Titrimetry
-Mass of the reagent is measured instead of its volume
Coulometric Titimetry
-The reagent is a constant direct electrical current of known magnitude that
consumes the analyte
- the time needed to complete the electrochemical reaction is measured

Types of Volumetric Titrations

1. Precipitation Titration
(Expt 4 Determination of the Chloride in the Sample)
2. Complexometric Titration
(Expt 5 Determination of the Total Hardness of
Commercial Mineral Water)
3. Redox Titration
(Expt 6 Determination of the Oxalate in the Sample)

PRECIPITATION TITRATION
-Based upon reactions that yield ionic compounds of limited
solubility
- one of the oldest analytical techniques dating to the mid-1800s
-The slow rate of formation of most precipitates, however, limits
the number of precipitating agents that can be used in titrations to
a handful
Argentometric Titrations- titrations with silver nitrate
Methods:
1. Volhard Method
2. Fajans Method
3. Mohr Method

Volhard Method
The Volhard method of Ag+ determination is associated with argentometric
titrations even though the titrating agent is actually SCN :
Volhard titration rxn
Ag+
+ SCN AgSCN(s)
analyte
titrant
The indicator in Volhard titrations is Fe3+, which reacts with titrant to form a
red- colored complex:
Volhard indicator rxn

Fe3+
+
indicator

SCNtitrant

Fe(SCN)2+(aq)
red complex

This is a good method for the analysis of Ag + in solution. We can extend the
applicability of this method to anions such as I through the procedure known
as back-titration. A measured excess of Ag+ is added to the dissolved sample:
Ag+
+ I
excess reagent analyte

AgI(s)

After the precipitation of AgI is complete, the concentration of

excess Ag+ titrant is determined by Volhard titration. The number
of moles of I analyte originally present in the solution is easily
calculated:
# mol I = # mol Ag+ originally added to solution # mol Ag+ as
determined by
Volhard titration
In a similar manner, the Volhard titration method can be used
to analyze for a number of anions.

The Fajans Method

Adsorption indicators function in an entirely different manner than the
chemical indicators described thus far, and they can be used in many
precipitation titrations, not just argentometric methods.
Ex. Determine the analyte Cl in a sample solution by titrating with Ag +; the
titration reaction would be
Ag+ + Cl AgCl(s)
Silver chloride forms colloidal particles. Before the equivalence point, the
surface of the precipitant particles will be negatively charged due to the
adsorption of excess Cl to the surface of the particles. A diffuse positive counterion layer will surround the particles. When the equivalence point is reached, there
is no longer an excess of analyte Cl, and the surface of the colloidal particles are
largely neutral.
After the equivalence point, there will be an excess of titrant Ag +, some of these
will adsorb to the solid AgCl particles, which will now be surrounded by a
diffuse negative counterion layer.

Adsorption indicators are dyes, such as dichlorofluorescein (shown below),

that usually exist as anions in the titration solution.

dichlorofluorescein
Adsorption indicator, an organic compound that adsorbs onto or desorbs
from the surface of the solid in a precipitation titration. Ideally,the adsorption or
desorption occurs near the equivalence point and results not only in a color
change but also in the transfer of color from the solution to the solid or vice
versa.
The doubly charged dichlorofluoroscein anion is attracted into the
counterion layer immediately following the equivalence point, when the surface
charge of the particles changes from negative to positive. For reasons that are
not fully understood, the closer proximity of the dye to the particles changes the
color of the molecule, providing a visual indication of the titration endpoint. In
the case of dichlorofluorescein, the indicator changes to a pinkish color.

Mohr Method
-Determination of chlorides by titration with silver nitrate
- oldest titration still in use
- researched and published by Karl Friedrich Mohr in 1856
- Chloride is titrated with silver nitrate AgNO3 in the presence of chromate
anions
- end point is signalled by the appearance of the red Ag 2CrO4

Titration reaction:
Ag+ + Cl- AgCl(s)

Ksp = 1 x 10-10

Indicator reaction:
2Ag+ + CrO42- Ag2CrO4(s)

Ksp = 1 x 10-12

Silver ions (from AgNO

solution) react with chloride ions (from the sample)
(reddish
3 brown)
and chromate ions (from the indicator) to form white precipitate of silver
chloride and red precipitate of silver chromate.

*Intense yellow color of chromate may make detection of first signs of

formation of silver chromate precipitate difficult.
-As some excess of Ag must be added before precipitate starts to form, if
concentration of titrant is below 0.1M, we may expect significant positive error.
- to correct for this error we can determine a blank, titrating a solution of the
indicator potassium chromate with standard silver nitrate.
- to make result more realistic, small amount of chloride-free CaCO3 was added
to the solution to imitate the Ag precipitate
AgNO3 photosensitive- decompose under the action of light
-Preferred base for black and white photographs for the 1 st 70 years or so
- when exposed to light, it decomposes to produce microscopic grains of Ag,
which appear black
2AgNO3 2Ag + 2NO2 + O2
Amber bottle- limit the amount and the range of light which enters the bottlereducing the extent of reaction

Solution during titration should be close to neutral (pH 7-10)

-In low pH, silver chromate solubility grows due to the
protonation of chromate anions
- in high pH, silver starts to react with hydroxide anions,
precipitating in the form of brownish AgOH and Ag2O, masking
the end point
- both processes interfere with the determination accuracy.
* Exactly the same approach can be used for determination of
bromides. Other halides and pseudohalides, like I- and SCNbehave very similarly in the solution, but their precipitate tends
to absorb chromate anions making end point detection difficult.

Complexometric
titrations

Many cations will form complexes in solution with a variety of

substances that have a pair of unshared electrons (e.g. On N, O, S
atoms in the molecule) capable of satisfying the coordination
number of the metal cation [metal cation is a Lewis acid (electron
pair acceptor) and the complex is a Lewis base (electron pair
donor)
The number of molecules of the complexing agent (ligand) will
depend on the coordination number of the metal cation and on the
number of complexing groups on the ligand molecule

Most metal ions react with electron-pair donors to form

coordination compounds or complexes.
*Ligand the donor species; has at least 1 pair of unshared eavailable to form covalent bond/s with a cation or neutral atom
- Chelating agent
*Coordination number the number of covalent bonds that a
cation tend to form
*Chelates a class of coordination compounds produced when a
metal ion coordinates with 2 or more donor groups of a single
ligand to form a 5-or 6-membered heterocyclic ring. (complex
formed)

Titration with a chelating agent is called a chelometric

titration, perhaps the most important and practical type
of complexometric titration.
Complexation reactions involve a metal-ion M
reacting with a ligand L to form a complex ML

M+L

ML

.
M + Ln-1

MLn

Most generally useful titrating agents are Aminocarboxylic acids,

in which amino nitrogen and carboxylate groups serve as ligands.
The amino nitrogens are more basic and are protonated
(-NH3+) more strongly than the carboxylate groups.
- When these groups bind to metal atoms, they lose their protons. The
metal complexes formed with these multidentate complexing agents
are often 1:1 regardless of the charge on the metal ion, because there
are sufficient complexing groups on one molecule to satisfy all the
coordination sites of the metal ion.

EDTA ( Ethylenediaminetetraacetic acid) most widely used

complexometric titrant.

- weak acid that can lose 4 H on complete neutralization

-Tetraprotic acid
-Hexadentate ligand
-The 4 acid oxygen sites and the 2 nitrogen atoms have unshared electron pairs,
which can form bonds to a metal ion forming a complex ion or coordination
compound
-The complex is quite stable, and the conditions of its formation can ordinarily
be controlled so that it is selective for a particular metal ion.

EDTA = H4Y
-The hydrogens in H4Y refer to the 4 ionizable hydrogens
belonging to the 4 carboxylic acid groups
-at sufficiently low pH, the nitrogens can also be protonated and
this diprotonated EDTA can be considered a hexaprotic acid.
However, this occurs at a very low pH and EDTA is almost never
used under such conditions
-It is the unprotonated ligand Y4- that forms complexes with metal
ions, that is, the protons are displaced by the metal ion upon
complexation
-Y4- combines with metal ions in 1:1 chemical equivalence
regardless of the charge of metal ions.

Chelon effect: The more complexing groups the better

Structure of EDTA-metal
complex

A: titration with a titradentate

ligand
B: titration with a bidentate
ligand
C: titration with a unidentate
ligand

The ability of EDTA to form complexes is affected by pH

The unprotonated form is a dominant species at very

basic solutions

EDTA titrations for Ca are displacement titrations.

Eriochrome Black T: triprotic (H3In)

Titrant (Mg-EDTA):
Mg2+ + H2Y2- (excess) MgY2- + 2H+

Titrand (Ca-EBT):
Ca2+ (excess) + H2In- CaIn-

(weak; pale red)

Titration:
Ca2+ + H2Y2- CaY2- + 2H+
Ca2+ + MgY2- CaY2- + Mg2+ (displacement)
CaIn- + H2Y2- CaY2- + H2InEnd point:
H2In- + Mg2+
MgIn- + H2Y2

MgIn- + 2H+

MgY2 + H2In-

(wine red)colorles(blue)

+ 2H+

Eriochrome Black
T

Water hardness
- is the total concentration of alkaline
which are mainly Ca2+ and Mg2+, in water.

earth

(Group

2)

ions,

-is commonly expressed as the equivalent number of milligrams of CaCO 3 per

liter.
-2 types of hardness:
a.) Temporary- due to presence of bicarbonates of Ca and Mg
- easily removed by boiling
b.) Permanent- due to presence of chlorides and sulfates of Ca and Mg
- cannot be removed by boiling

Water Hardness: Good and Bad

Bad

Good

Difficulty in lathering soap and the

formation of a scum in the bath tub

Beneficial to irrigation

Scale build up in pipes and electric

heating elements

Not known to be unhealthy

-Reduce risk of cardiovascular
diseases.
- useful for growth of children due
to presence of Ca

Gray staining of washed clothes

M2+ + EDTA4- [M-EDTA]2- + 2H+

(the H+ comes from the EDTA)
The important point is that the reaction is 1:1

EDTA, M2+, and M-EDTA are all soluble and colorless.

We need a secondary indicator a second chemical reaction that will result in
some visible change.
Calmagite or Eriochrome Black T are blue dyes when alone in water. When it
is complexed with a Metal ion, it turns red.
EBT- forms a very stable wine red complex, MgIn -, with the magnesium ion.
- A tiny amount of this complex will be present in the solution during the
titration
-As EDTA is added, it will complex free Ca 2+ and Mg2+ ions, leaving the MgIncomplex alone until essentially all of the Ca and Mg have been converted to
chelates
- At this point, EDTA concentration will increase sufficiently to displace Mg 2+
from the indicator complex; the indicator reverts to its uncombined form,
which is sky blue, establishing the end point of the titration

EDTA titration
Initially (before EDTA is added):
M2+ + dye (blue) M2+ - dye (red)
When you begin to add EDTA:
M2+ + EDTA M-EDTA
M2+ + dye (blue) M2+ - dye (red)
At equivalence ([EDTA]=[M]):
M2+ + EDTA M-EDTA
Dye (blue)
This only works if
the EDTA binds the metal better than the indicator!

Titration is carried out at pH 10, in a NH3/NH4+ buffer, which keps the EDTA
(H4Y) mainly in the form HY3-, where it complexes the Group2 ions very well
but does not tend to react as readily with other cations such as Fe 3+ that might
be present as impurities in the water
Titration
HY3- (aq) + Ca2+ (aq) CaY2- (aq) + H+ (aq)
End Point
HY3- (aq) + MgIn- (aq) MgY2- (aq) + HIn2- (aq)
wine red
sky blue
Since the indicator requires a trace of Mg 2+ to operate a little magnesium ion
will be added to each solution. The effect of the added Mg 2+ can be subtracted
by titrating a blank

Redox Titrations

Three types of visual indicators are used to signal the end point in a
redox titration.

Self-indicators: titrants that have oxidized and reduced forms

whose colors in solution are significantly different (e.g., MnO4-)
Specific indicators: substances that indicate the presence of a
specific oxidized or reduced species (e.g., starch, thiocyanate)
Redox indicators: weak reducing or oxidizing agents that can be
oxidized or reduced; the colors of the oxidized and reduced forms
are different

Ideal indicator: transition potential should fall within the steep equivalence point
break.

KMnO4 is a strong oxidizing agent (E = 1.51V)

MnO4- has intense dark purple color
The reduction of purple MnO4- to the colorless Mn2+, the solution will turn from dark purple to a
faint pink color at the equivalence point
*No additional indicator needed; KMnO4 reacts as a self-indicator for the end-point detection
Reduction of permanganate requires strong acidic conditions
- permanganate is reduced by oxalate, C2O42- in acidic conditions
Oxalate reacts very slowly at room temp., so the solutions are titrated hot to make the procedure
practical
MnO4- + C2O42- Mn2+ + CO2
In neutral solution, the reduction product of this permanganate is MnO 2, rather than Mn2+
-The MnO2 acts as a catalyst for further decomposition of the permanganate, which produces
more MnO2, and so on. This is called Autocatalytic Decomposition.

Interference:
4MnO4- + 2H2O 4MnO2 + 3O2 + 4OH(catalyzed by light, heat, acids, bases, MnO2, Mn2+)

Determination of Oxalate
Is important because it is toxic. The
toxicity of oxalic acid is due to kidney
failure caused by precipitation of
solidcalcium oxalate.
Oxalic acids main applications include
cleaning and bleaching especially in
removal of rust
Redox half reactions:
H2C2O4 CO2 + 2H++ 2e-

Calculation for redox titration is also stoichiometric,

but balance first the chemical reaction
Standardization:

[titrant] = mass of standard x x stoichiometric

ratio x
Determination of analyte:
% (w/w) analyte = volume of titrant* x [titrant]
x stoichiometric ratio
x Manalyte x
*Corrected volume by performing blank determination