TITRIMETRIC METHODS

OF ANALYSIS
Volumetric Titrimetry – involves measuring the volume
of a solution of known concentration that is needed to
react essentially and completely with the analyte.

Gravimetric Titrimetry – differs only in that the mass of

the reagent is measured instead of its volume.

CoulometricTitrimetry – the reagent is a constant direct

electric current of known magnitude that is directly or
indirectly reacts with the analyte, here, the time
required to complete the electrochemical reaction is
measured.
 Titrimetric methods of analysis are capable of rapid and
convenient analyte determinations with high accuracy and
precision. Titrimetric analysis is based on the complete
reaction between the analyte and a reagent, the titrant:

aA + tT→ products

where A and T represent the analyte and titrant,

respectively, and a and t are the stoichiometric coefficients.
Titrations are often classified by the nature of this titration
reaction: acid-base, redox, precipitation and complexation
reactions are the most common reaction types.
Quantitative determination of the analyte concentration
requires the following:

1. There is a stoichiometric reaction between analyte and

titrant. This reaction should be fast and complete, and
the values of a and t must be known.

2. The concentration of the titrant solution, CT, must be

known accurately. The titrant solution must be
standardized either by preparing it using a primary
standard or, more commonly, titrating it against a
solution prepared with a primary standard.
3. The endpoint volume must be measured accurately
using an appropriate chemical indicator or instrumental
method. If an instrumental method is used to follow the
progress of the titration reaction, a titration curve may
be generated, which allows for the analysis of mixtures
and/or the detection of interferences.
Standard solution is a reagent of exactly known
concentration that is used in a titrimetric analysis.

Primary standard is an ultrapure compound that serves

as the reference material for a titrimetric method of
analysis.
 Requirements:

1. high purity, preferably 99.9% or better; established

methods for confirming purity should be available.
2. stability towards air
3. absence of water of hydration so the composition of the
solid does not change with variation in humidity
4. ready availability at modest cost
5. reasonable solubility in the titration medium
6. reasonably large molar mass so that the relative error
associated with weighing the standard is minimized
 Secondary standard is a compound whose
purity has been established by chemical analysis
and that serves as the reference material for a
titrimetric method of analysis.

 Titration is a process in which a standard

reagent is added to a solution of an analyte until
the reaction between the analyte and the reagent
is judged to be complete.
Back-titration
- a process in which the excess of a standard
solution used to consume an analyte is determined
by titration with a second standard solution.
Back titrations are often required when the
rate of reaction between the analyte and reagent
is slow or when the standard solution lacks
stability.
Standardization
- a process in which the concentration of a
volumetric solution (secondary standard) is
determined by using it to titrate a known mass of
a primary standard or an exactly known volume of
another secondary standard solution.
The equivalence point is the point in a titration
when the amount of added standard reagent is
exactly equivalent to the amount of analyte.

The end point is the point in a titration when a

physical change occurs that is associated with the
condition of chemical equivalence.

 The difference in volume or mass between the

equivalence point and the end point is the
titration error
titration error: Et = Vep - Veq
The ideal standard solution for titrimetric method will:
1. be sufficiently stable so that it is only necessary to
determine its concentration once.
2. react rapidly with the analyte so that the time
required between the additions of reagent is
minimized.
3. react more or less completely with the analyte so
that satisfactory endpoints are realized.
4. undergo a selective reaction with the analyte that
can be described by simple balanced equation.
1. Direct Method – here, a carefully weighed quantity of
a primary standard is dissolved in a suitable solvent
and diluted to an exactly known volume in a
volumetric flask.

2. Standardization – here, the titrant to be standardized

is used to titrate:
a. a weighed quantity of primary standard,
b. a weighed quantity of secondary standard, or
c. a measured volume of another standard solution.
 Acid-base titration is based on the
neutralization reaction between the analyte and an
acidic or basic titrant.
These most commonly use a pH indicator, a
pH meter, or a conductance meter to determine
the endpoint.
 Redox titration is based on an oxidation-
reduction reaction between the analyte and titrant.
These most commonly use a potentiometer
or a redox indicator to determine the endpoint.
Frequently either the reactants or the titrant have
a color intense enough that an additional indicator
is not needed.
Ex. titration of potassium permanganate
 Complexometric titration is based on the
formation of a complex between the analyte and
the titrant.
The chelating agent, EDTA, is very commonly
used to titrate metal ions in solution. These
titrations generally require specialized indicators
that form weaker complexes with the analyte. A
common example is Eriochrome Black T for the
titration of calcium and magnesium ions.
Ways of Expressing Concentration of Solutions:

1. Mass percentage
mass % of component =

2. Volume percentage
volume % of component =
3. Parts per million, ppm (for very dilute solutions)

ppm component =

= 1mg/kg solution = 1mg/L solution = 1g/mL

parts per billion, ppb =

= μg/L solution
4. mole fraction, 

=

5. Molality, m (does not vary with temperature)

m= (mol/kg)
6. Molarity, M

M= (mol/L)

7. Normality, N

N= (eq/L)

where # of equivalents =

EW = =
 a= = depends on the nature of the
solute

when the solute participates in:

a. acid-base reaction:
a = number of replaceable H+ or OH- per mole of an acid/base
equivalent weight = amount of substance that reacts with
or supplies 1 mole of H+ ions in the given reaction

Ex. HCl a = 1 eq/mol→ EW = 36.46 g/eq

H2SO4 a = 2 eq/mol→ EW = 98.08 g/2eq = 49.04 g/eq
NaOH a = 1 eq/mol
Ba(OH)2 a = 2 eq/mol
b. precipitation/complex formation:
a = based on the number of univalent cation

equivalent weight = amount of substance that reacts with

or supplies 1 mol of univalent cation (1/2 mol of
divalent cation, 1/3 mol of trivalent
cation, and so on)
Ex. KCl: K+ and Cl- a = 1 eq/mol
Ca(NO3)2: Ca2+ and NO3- a = 2 eq/mol

Ag+ + 2CN–→ Ag(CN)2– EW (Ag+)=FWAgNO3/1;

EW(CN–) = 2FWCN/1
c. redox reaction:
a = total number of electrons gained or lost during redox
reactions
equivalent weight = amount of substance that directly or
indirectly produces 1 mole of electron

Ex. C2O42- → CO2 a = 2 eq/mol

MnO4- → Mn 2+ a = 5 eq/mol
 M = ; N=

hence,
Dilution of Solution

When a solution is diluted:

the volume is increased by adding more solvent,
the concentration is decreased, and
the total amount of solute remains constant

Dilution Formula: C1V1 = C2V2

where C1 = initial concentration
V1 = initial volume
C2 = final concentration
V2 = final volume
1. A standard 0.0100M solution of Na+ is required to calibrate a flame
photometric method to determine the element. How many grams primary
standard Na2CO3 (105.99 g/mol) is required to prepare 500 mL of this
solution?
2. How would you prepare 50.0 mL portion of standard solution that is
0.00500 M in Na+ from the above solution?
3. A 50.00 mL portion of an HCl solution required 29.71 mL of 0.01963 M
Ba(OH)2 to reach an endpoint with bromcresol green indicator. Calculate the
molarity of HCl.
4. Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol) required 43.31 mL of
KMnO4. What is the molarity of the solution?
5. A 0.8040 g sample of an iron ore is dissolved in acid. The iron is the
reduced to Fe2+and titrated with 47.22 mL of 0.02242 M KMnO4 solution.
Calculate the results of this analysis in terms of:
a) %Fe (55.847 g/mol) and
b) %Fe3O4 (231.54 g/mol).

The reaction of the analyte with the reagent is:

MnO4- + 5Fe2+ + 8H+→ Mn2+ + 5Fe3+ + 4H2O
b) % Fe3O4 (231.54 g/mol).

The reaction of the analyte with the reagent is:

MnO4- + 5Fe2+ + 8H+→ Mn2+ + 5Fe3+ + 4H2O
6. A 100.0-mL sample of brackish water was made ammoniacal, and the sulfide
it contained was titrated with 16.47 mL of 0.02310 M AgNO3. The analytical
reaction is 2Ag+ + S2-→ Ag2S (s). Calculate the concentration of H2S in ppm.
7. The phosphorus in a 4.258-g sample of a plant food wasconverted to PO43-
and precipitated as Ag3PO4 through the addition of 50.0 mL of 0.0820 M
AgNO3. The excess AgNO3 was back-titrated with 4.06 mL of 0.0625 M KSCN.
Express the results of this analysis in terms of %P2O5.
8. The CO in a 20.3-L sample of gas was converted to CO2 by passing the gas
over I2O5 to 1500C:
I2O5(s)+ 5CO(g)→ 5CO2(g) + I2(g)

The iodine was distilled at this temperature and was collected in an absorber
containing 8.25 mL of 0.01101 MNa2S2O3 with this reaction;

I2(g) + 2S2O32-(aq)→ 2I-(aq) + S4O62-(aq)

The excess Na2S2O3 was back-titrated with 2.16 mL of 0.00947 M I2 solution.

Calculate the concentration in mg of per L of sample.
9. A 300.0-mg sample containing H3PO4 and inert material was diluted with
water and titrated with 0.05000 M NaOH. According to the reaction,
H3PO4 + 2NaOH → Na2HPO4 + 2H2O.
The endpoint was reached after 29.00 mL of titrant was added. Calculate the
%H3PO4 in the sample.
10. Exactly 600.0 mg of pure Na2C2O4 was dissolved in acid and titrated with a
KMnO4 solution according to the reaction;
2MnO4- + 5C2O42- + 16H+→2Mn2+ + 10CO2(g) + 8H2O
end point was reached after adding 34.00 mL of titrant. Calculate the molarity
of the KMnO4.
11. A 750.0-mg sample of iron ore was dissolved in acid and treated to oxidize
all of the iron to Fe3+ ion. After destroying remaining oxidizing agent, excess KI
was added. The liberated I2 required 18.50 mL of 0.07500 M Na2S2O3 for
titration. What is the %Fe in the sample?
2Fe3+ + 2I-→ 2Fe2+ + I2
I2+ 2S2O32-→ 2I- + S4O62-
12. A Na2S2O3 solution is standardized by weighing and dissolving 250.0 mg of
pure copper metal. The copper solution is treated with excess KI and the
liberated I2 requires 44.90 mL of the thiosulfate titrant to reach the
end point. What is the molarity of the Na2S2O3?
2Cu2+ + 4I- (excess) → 2CuI(s) + I2
I2 + 2S2O32- → 2I-+ S4O62-
13. An 800.0-mg sample of Cr ore was dissolved and the Cr oxidized to
chromate ion. The solution was treated with10.00 mL of 0.2000 M AgNO3. The
resulting precipitate of AgCrO4 was removed and discarded. The excess AgNO3
required 14.50 mL of 0.1200 M KSCN for titration. Calculate %Cr2O3 in the ore.
CrO42- + 2Ag+ → Ag2CrO4 (s)
Ag+(excess) + SCN-→ AgSCN(s)
14. A 0.2638-g soda ash sample is analyzed by titrating the sodium carbonate
with the standard 0.1288 M HCl, requiring 38.27 mL. The reaction is
CO32- + 2H+ → H2O + CO2
Calculate %Na2CO3 in the sample.
15. How many mL of 0.25M solution of H2SO4 solution will react with 10 mL of a
0.25M solution of NaOH? The reaction is :
H2SO4 + 2NaOH → Na2SO4 + 2H2O
16. A sample of impure salicylic acid, C6H4(OH)COOH (one titrable proton), is
analyzed by titration. What size sample should be taken so that the percent
purity is equal to five times the milliliters of 0.0500M NaOH used to titrate it?
17. The iron(II) in an acidified solution is titrated with 0.0206M solution of
KMnO4 :
5Fe2++ MnO4- + 8H+→ 5Fe3+ + Mn2+ + 4H2O
If the titration required 40.2 mL, how many mg Fe are in the solution?
18. Aluminum is determined by titrating with EDTA:
Al3+ + H2Y2-→AlY- + 2H+
A 1.00-g sample requires 20.5 mL EDTA for titration. The EDTA was
standardized by titrating 25.0 mL of a 0.100 M CaCl2 solution, requiring 30.0
mL EDTA. Calculate %Al2O3 in the sample.