Analytical Chemistry Notes Titrations

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE
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TOPIC 1
GENERAL PRINCIPLES OF TITRATION
Titration is a process in which a standard reagent is added to a solution of analyte until the
reaction between the analyte and reagent is judged to be complete.
The standard solution is called the titrant; the volume of titrant needed for the titration is
carefully measured by means of a buret. The titrand refers to the solution to be titrated by a
standard solution.
1.1 Criteria for a Successful Volumetric Analysis

2. The reaction should be stoichiometric; that is, there should be a definite whole-number ratio
between a and b in the reaction: aA + bB products
3. The rate of chemical reaction should be rapid so that titration can be carried out quickly.
4. The reaction should be quantitative, that is, it must be at least 99.9% complete when a
stoichiometric amount of titrant has been added.
5. Some method must be available for determining the point in the titration at which a stoichiometric
amount of titrant has been added and the reaction is complete.
Change in color of indicator
Change in physical properties of the solution
Change in the electrochemical properties
1.2 Equivalence Points, End Points and other Terminologies
Indicators are often added to the analyte solution to give an observable physical change (the
end point) at or near the equivalence point.
The end point is the point in a titration when a physical change occurs that is associated with
the condition of chemical equivalence.
The equivalence point is the point in a titration when the amount of added standard reagent is
equivalent to the amount of analyte. The equivalence point of a titration cannot be determined
experimentally.
The difference in volume or mass between the equivalence point and the end point is the
titration error: Et = Vep Veq

Where
Veq = theoretical volume required to reach the equivalence point
Vep = actual volume used to arrive at the end point
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Analytical Chemistry Review Notes 1

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Provided that the end point coincides with the equivalence point, the amounts of titrant and
titrand measured should correspond to the actual amounts present. In some cases, the end
point detected does not correspond exactly with the equivalence point. This
may be due to problems with the reaction, or to the small amount of reagent
needed to react with additional materials (for example, the added indicator) present in the titrand.
In these cases, a blank titration must be performed, or allowance made for the titration error.
1.3 Standard Solutions

A standard solution (titrant) is a reagent of known concentration that is used in a titrimetric
analysis.
Direct method. A carefully weighed quantity of a primary standard is dissolved in a suitable
solvent and diluted to a known volume in a volumetric flask.
Standardization method. Prepare a stock solution of approximately known concentration and
then to standardize it by titrating a known amount of some primary standard with this solution.
1.4 Desirable Properties of Standard Solutions
The ideal standard solution for a 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 additions of reagent is minimized
3. React completely with the analyte so that satisfactory end points are realized
4. Undergo a selective reaction with the analyte that can be described by a balanced equation.
1.5 Primary Standards
A primary standard is a highly purified compound that serves as a reference material in all
volumetric and mass titrimetric methods. The important requirements for a primary standard
are:
1. High purity (established methods for confirming purity should be available)
2. Atmospheric stability
3. Absence of hydrate water so that the composition of the solid does not change with variations
in relative 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.
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1.6 Scope of Titration
1. Precipitation Titrimetry. Determination of chloride by titration with standard solution of a silver
salt:
Ag+ + Cl- AgCl(s)
- Endpoint can be detected by any visual indicator.
2. Neutralization Titrimetry (Acid-Base)
OH- (titrant) + HA (acid titrated) A- + H2O
H+ (titrant) + B (base titrated) BH+
- Endpoint can be detected by any suitable indicator or a pH meter
3. Complex- Formation Titrimetry
M+ (metal ion to be titrated) + EDTA (L; as titrant) ML
- Endpoint can be determined with a color change using a suitable indicator
4. Oxidation Reduction Titrimetry
-several elements that have more than one oxidation states can be determined by titration with
standard oxidizing or reducing agents. Example: MnO4- + 5Fe2+ + 8H+ 5Fe3+ + Mn2+ + 4H2O, the end
point is detected by permanent violet color. The endpoints in REDOX titrations are determined by
means of visual indicators.
1.7 Volumetric Calculations with Molarity
Mole: A mole is the formula weight of the substance expressed in grams (moles = g / FM)
Molarity: the molar concentration M of a solution is the number of moles of solutes present in
one liter of solution (M = mole / L-soln. )
Millimole: A millimole is the formula weight of the substance expressed in milligrams (mmole =
mg / FM)
Molarity: the molar concentration M of a solution is the number of millimoles of solutes present in
one milliliter of solution (M = mmole / mL-soln. )
Dilution Formula : M1 V1= M2 V2
A helpful tool! x(Macid Vacid) = y(Mbase V base) where x and y are stoich coefficient in a balanced
reaction.
EXERCISES
1.
What volume of concentrated (12.0 M) hydrochloric acid should be used to prepare 500 mL of
0.100 M HCl stock solution?
2.
A given sample containing sodium iodide requires 26.20 mL of 0.1000 M hydrochloric acid for
titration according to the reaction, 2HCl + Na2CO3 products. Calculate the weight in milligrams of
sodium carbonate.
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3.
Exactly 410.4 mg of primary standard potassium acid phthalate (KHP), formula weight 204.2, is
weighed out and dissolved in water. If titrating the KHP requires 36.70 mL of sodium hydroxide
solution, what is the molarity of sodium hydroxide? OH- + HP- P2- + H2O
1.8 Volumetric Technique: Back Titration

Back-titration is 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
(1) the rate of reaction between the analyte and reagent is slow.
(2) when the standard solution lacks stability.
aA (titrant) + bB (subs. titrated) products + excess A
cC (back titrant) + dA (excess) products
Some useful Formulas:
mmol reagent reacted = mmol taken mmol back-titrated
mg analyte = mmol reagent reacted
x factor x FM analyte
where
factor = mmol analyte / mmol reagent
FM = (mg/mmol)
EXERCISES
1. Back titration in Complex-Formation Titration: Zirconium (IV) reacts rather slowly with EDTA and
must be determined using back titration. Exactly 10.00 mL of 0.0502 M EDTA is added to a solution
containing zirconium (IV). Back-titration of the excess EDTA requires 2.08 mL containing 0.0540 M
bismuth nitrate. Calculate the weight of zirconium in the solution.
2.
Back titration in Neutralization Titration: The ethyl acetate concentration in an alcoholic solution
was determined by diluting a 10.00-mL sample to 100.0 mL. A 20.00-mL aliquot of the diluted
solution was refluxed with 40.00 mL of 0.04672 M KOH: CH3COOC2H5 + OH- CH3COO- + C2H5OH
After cooling, the excess OH- was back-titrated with 3.41 mL of 0.05042 M H2SO4. Calculate the
number of grams ethyl acetate (FM = 88.11 g/mol) per 100 mL of the original solution.
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3. Back titration in REDOX Titration: A 0.200-g sample of pyrolusite is analyzed for manganese content
as follows: Add 50.0 mL of a 0.100 M solution of ferrous ammonium sulfate to reduce the MnO2 to
Mn2+ . After reduction is complete, the excess ferrous ion is titrated in acid solution with 0.0200 M
KMnO4, requiring 15.0 mL. Calculate the percent manganese in the sample as Mn 3O4.
The reaction between Fe2+ and MnO4- is: 5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
The reaction between Fe2+ and MnO2 is: MnO2 + 2Fe2+ + 4H+ Mn2+ + 2Fe3+ + 2H2O
1.9 Volumetric Calculations with Normality
At the stoichiometric point of titration (i.e equivalence point), the milliequivalents of titrant A
always equals the milliequivalents of titrated substance B. The combining ratio B to A used in the
molar system has been taken into account in preparing normal solutions.
NA VA = NB VB
(eq/L)A L A = (eq/L)B LB
The advantage of expressing concentrations in normality and quantities as equivalents is that one
equivalent of substance A will ALWAYS react with one equivalent of substance B.
Example: One equivalent of NaOH ( 1 mol) will react with one equivalent of HCl (1 mol).
One equivalent of NaOH (1 mol) will react with one equivalent of H2SO4 (1/2 mol).
It must be emphasized that the number of equivalents, or normality DEPENDS upon a specific
reaction:
Example: Na2CO3 may react with either
one (1) H+ in the reaction CO32- + H+ HCO3two (2) H+ in the reaction CO32- + 2H+ H2CO3
Thus, there is a danger in using normality, equivalents, and equivalent weight that is they are entirely
dependent on the particular reaction, and this must be specified. Another example: Consider 0.100 N
solution of KMnO4:
Under acid solution: MnO4 - + 8H+ + 5e- Mn2+ + H2O
Under basic solution:MnO4- + 2 H2O + 3e- MnO2 + 4OHThe first reaction corresponds to a 5 electron change, and the second reaction involves a three electron
change. Normality depends on the knowledge and availability of the balanced reaction, whereas
Molarity does not. A 0.1 M KMnO4 solution is always 0.1 M, but it can be 0.5 N or 0.3 N solutions
depending on how it was used.
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Some Useful Formulas in using Normality:
If A is the sample (analyte) which is titrated by substance T :
A general equation can be used to calculate the percent of a constituent in the sample:
EXERCISES
1. A hydrochloric acid solution is standardized by titration with standard sodium hydroxide. If 25.00 mL
of HCl requires 32.20 mL of 0.0950 N NaOH for Titration, what is the normality of the HCl solution?
2. A 150.0 mg sample of pure sodium carbonate (Na 2CO3) requires 30.06 mL of hydrochloric acid
solution for titration: 2H+ + CO32- CO2(g) + H2O Calculate the normality of hydrochloric acid?
3. A 0.2000 g sample of a metal alloy is dissolved, and the tin is reduced to tin (II). Titration of the tin (II)
requires 22.20 mL of 0.1000 N K2Cr2O7. Calculate the percentage of tin in the alloy. The tin is oxidized from
22+
+
4+
3+
tin(II) to tin(IV) in the reaction: Cr2O7 + 3 Sn + 14H 3Sn + 2Cr + 7 H2O
4. Consider the following data:

Sample = 0.03500 g; HCl used = 48.03 mL; NaOH used for back titration = 2.02 mL
Standardization: 1.000 mL of HCl required 0.00530 g Na2CO3 (FM 106.00)
1.000 mL of NaOH required 0.02192 g KHC2O4.H2O (FM 146.13)
Reactions:
2 HCl + Na2CO3 products
and
NaOH + KHC2O4.H2O products
(a) Calculate the concentrations of the standard HCl and NaOH solutions in normality
(b) Calculate the alkaline strength of pearl ash (impure potassium carbonate) in terms of percent K 2O
K2O + 2HCl products
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TOPIC 1 ASSESMENT
MULTIPLE CHOICE Choose the letter that best describes or answers the question. Provide all necessary
solutions for items requiring computations on the spaces provided for each number. Erasures will invalidate
your answer.
_____1. In considering a reaction for titrimetric analysis, the following factors should be seriously considered,
Except?
A) Chemical reactions must take place rapidly and proceed to completion at the equivalence point
B) Chemical reactions must be stoichiometric, that is, the titrant should react with the analyte in a 1:1 ratio
C) Chemical reactions must be at least 99% complete when stoichiometric amount of the titrant has been added
D) Chemical reactions must be proceed according to a definite chemical equation.
_____2. An analyst was commissioned to determine the concentration of substance X present in a solution. He
was provided with some data about X and as a result decided that a simple volumetric analysis would not yield a
very accurate result. Which one of the following properties of X may have influenced this decision?
A. Weak reductant
B. Soluble in water
C. Highly volatile
D. Colorless
_____3.This type or volumetric error happen whe you transfer too much indicator to your titration medium.
A. Endpoint error
B. equivalence point error
C. titration error
D. indicator
error
_____4.To standardize a supplied sodium hydroxide solution, a pair of students placed the base in a burette and
titrated it against a standard potassium hydrogen phthalate solution, KH(C8H4O4), which was previously prepared
using a 250-mL volumetric flask. Which items of equipment should the students have rinsed out with several
amounts of de-ionised water just before use, and with no other chemicals, during this procedure?
A. The volumetric flask and reaction flask only
C. The reaction flask only
B. The pipette and burette only
D. All of the apparatuses
_____5.Which of the following statements are correct?

(1) A specific volume of analyte is transferred into a conical flask for titration by a pipette.
(2) The titrant is run from the burette into the conical flask.
(3) Precipitation titration is a type of volumetric analysis.
A. (1) and (2) only
C. (2) and (3) only
B. (1) and (3) only
D. (1), (2) and (3)
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_____6. A 25 mL aliquot of HCl is taken from a 250 mL volumetric flask containing 0.2 M HCl. Compared to the
solution in the volumetric flask, the aliquot will have ...
A) The same pH but one tenth the concentration of HCl.
C) The same pH and same number of
mole of HCl.
B) The same pH but one tenth of th e mole of HCl.
D) A pH that has increased by one.
_____7.In a volumetric analysis of vinegar to determine the concentration of ethanoic acid present, a pair of
students obtained the following results:
Initial burette reading (mL)
0.10
0.15
0.00
0.25
0.30
Final burette reading (mL)
22.70
22.60
22.50
22.73
22.60
The mean titre is:
A. 22.60 mL
B. 22.48 mL
C. 22.477 mL
D. 22.47 mL
_____8. Properties of a primary standard for use in acid-base titrations include...
A) low molar mass and low solubility.

B) high purity and low solubility.
C) reactive with oxygen and low molar mass.

D) stability and high purity
_____9.Which one of the following substances is not suitable for use as a primary standard in volumetric
analysis?
A. Sulfuric acid
B. Potassium hydrogen phthalate.
C. Oxalic acid. D. Anhydrous sodium
carbonate
_____10. Bases such as NaOH and KOH are not classified as primary standard because
A) They contain carbonate and adsorbed water

masses
C) They have relatively low molecular
B) They have limited solubility in the titration medium

moderate cost
D) They are not readily available at
_____11.What term is used to describe a substance that, when exposed to air, absorbs so much water from the
air that it eventually forms a solution?
A. Hydrated
B. Efflorescent
C. Hygroscopic D.
Deliquescent
_____12. Which of the following is not a good practice to prepare standard KOH and NaOH Solutions?
A) The water used to dissolve NaOH and KOH pellets should be boiled
B) Solutions of NaOH and KOH solutions show be kept in tightly covered polyethylene bottles
C) Strongly basic solutions of KOH and NaOH should not be kept in buret longer than necessary
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D) Solutions NaOH and KOH solutions must be stored in glass containers
_____13.Which is true about the equivalence point in an acid-base titration?
A)
B)
C)
D)
The [H3O+] ion concentration equals Ka of the acid

The [H3O+] ion concentration equals the Ka of the indicator
The amount of acid and base which have been combined are in stoichiometric ratio
The occurrence of a faint pink coloration using phenolphthalein as indicator
_____14. In the standardization of an acid solution with sodium carbonate, why is it necessary to boil the
solution before completing the titration?
A) To eliminate the reaction product, carbon dioxide and carbonic acid

B) To destroy the buffering action of the solution due to the presence of carbonic acid and unreacted
hydrogen carbonate
C) To achieve a sharper end point due to the large decrease in pH
D) All of the above reasons are correct.
_____15. Why is HNO3 seldom used to prepare standard acid solutions?
A)
B)
C)
D)
It is a oxidizing agent and will react with reducible species in the titration medium
The acid will react with the titrant
It usually reacts with CO2 from the atmosphere
Commercially available HNO3 contains a considerable degree of impurities
_____16.Two pairs of students were analysing the same sodium hydroxide solution by titrating 20.00 mL aliquots
against the same standard solution of potassium hydrogen phthalate. The first pair obtained a mean titre of
21.45 mL while the second pair obtained a mean titre of 21.80 mL. Which of the following might explain the
difference in the mean titres?
A. The first pair rinsed their burette with only water and not acid.
B. The second pair rinsed their burette with only water and not acid.
C. The NaOH used by the second pair had absorbed more CO2 out of the air.
D. The first pair blew the last drop of base out of their pipette.
_____17.An experimental value for the concentration of hydrochloric acid in a sample of toilet cleaner was
obtained by titrating a diluted solution of the toilet cleaner against a standard solution of anhydrous sodium
carbonate. This experimental value was found to be lower than that claimed by the manufacturer. Which one of
the following explanations offered by different students could reasonably account for this difference?
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A. Some HCl gas evaporated from solution during the analysis.
B. The toilet cleaner may have absorbed carbon dioxide out of the air.
C. The Na2CO3 used contained some water of hydration.
D. The pipette was rinsed out with water instead of Na2CO3 solution.
_____18.A 500.0 cm 3 potassium chloride solution was prepared by dissolving potassium chloride in distilled
water. 25.0 cm 3 of the solution was titrated with 0.300 M silver nitrate solution. 28.90 cm 3 of silver nitrate
solution was required to reach the end point in the titration. What is the number of moles of potassium chloride
present in the 500.0 cm 3 solution? A. 0.009 mol
B. 0.029 mol
C. 0.173 mol
D. 8.670
mol
_____19.An impure sample of anhydrous sodium carbonate was analysed as follows. Several 1.000 g samples of
the impure mixture were weighed out into separate conical flasks and about 20 mL of distilled water was added
to each. The mixtures were stirred and then 4 drops of an acidbase indicator were added to each flask. These
were then standardized against hydrochloric acid of concentration 0.1542 mol L-1, according to the reaction:
Na2CO3(aq) + 2HCl(aq)
2NaCl(aq) + H2O(l)
Three concordant results were obtained for the titres: 21.25 mL, 21.29 mL and 21.30 mL. The percentage purity
of the sodium carbonate was:
A. 8.696%
B.17.39%
C. 17.90%
D. 34.78%
_____20.The alcohol content of a certain low alcohol beer was determined using volumetric analysis. In this
analysis, a 10.00-mL sample of the beer was pipetted into a 100-mL volumetric flask and the solution was made
up to the mark. Then 20.00 mL aliquots of this solution were titrated against acidified potassium dichromate
solution, K2Cr2O7 of concentration 0.0500 mol L-1. A mean titre of 16.35 mL was obtained. The equation for the
analysis is:
2Cr2O72-(aq) + 3C2H5OH(aq) + 16H+(aq)
4Cr3+(aq) + 3CH3COOH(aq) + 11H2O(l)
What was the molarity of the alcohol in the beer?

A. 0.0273 mol L-1
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B. 0.0613 mol L-1
C. 0.273 mol L-1
D. 0.613 mol L-1

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PROBLEM SOLVING Solve what is being asked for in each of the problems. Present logically your solution and
express your answers using in 4 significant figures with their proper units. Enclose all final answers.
1) A 0.4755-g sample containing (NH4)2C2O4 and inert compounds was dissolved in water and made
alkaline with KOH. The liberated ammonia (NH3) was distilled into 50.00 mLof 0.1007 N H2SO4. The
excess H2SO4 was back-titrated with 11.13 mL of 0.1214 N NaOH. Calculate the percentage of N
(FM=14.007) and of (NH4)2C2O4 (FM=124.10). Hint: Write and balance all pertinent chemical
reactions first.
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TOPIC 2
NEUTRALIZATION TITRATIONS
1.1 Introduction
Neutralization titrations involve the reaction between the analyte and titrant in an acid base reaction.
The standards solutions used as titrants for unknown weak acids or bases are always strong bases or
acids, respectively.
Standard titrant acids: dilute solutions of HCl, HClO4 and H2SO4 (why is HNO3 not used???)
Standard titrant bases: dilute solutions of NaOH, KOH.
Primary standards: potassium acid phthalate (KHP), sodium oxalate, sodium bicarbonate.
Standardizing Acid Solutions
Acids are frequently standardized against
weighed quantities of sodium carbonate Na2 CO3.
There are two end points are observed in the

titration of sodium carbonate with an acid.
The second end point is always used for

standardization.
An even sharper end point can be achieved by

boiling the solution briefly to eliminate the
reaction products.
Tris-(hydroxymethyl)aminomethane, (HOCH)CNH, known also as TRIS or THAM, is also

available in primary-standard. It possesses the advantage of a substantially greater mass per
mole of protons consumed (121.1) than sodium carbonate
Standardizing Base Solutions
Potassium Hydrogen Phthalate, KHCHO
Non-hygroscopic crystalline high molar mass (204.2 g /mol)
Other Primary Standards for Bases:
Benzoic acid is obtainable in primary-standard purity
Potassium hydrogen iodate, KH(IO)
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Practical Notes in preparing Base Solutions

NaOH and KOH are not primary standards because they contain carbonate (from reaction with
atmospheric CO2) and adsorbed water.
Solutions of KOH and NaOH must be standardized against a primary standard such as KHP.
Distilled water, should be boiled briefly to eliminate the dissolved CO2 gas. The water is then
allowed to cool because hot alkali solutions rapidly absorb carbon dioxide. Alkaline solutions must
be protected from the atmosphere otherwise they absorb CO 2:OH- + CO2 HCO3CO2 changes the concentration of the strong base over a period of time and decreases the extent
of reaction near the end point in the titration of weak acids.
KOH and NaOH solutions must be kept in tightly capped polyethylene bottles with screw caps (avoid
storing strong base solutions in glass bottles).
Strong base solutions should not be kept in a buret longer than necessary.
Scope of Acid Base Titrations:
1. Strong Acid titrated with a Strong Base
3. Titration of a Weak Base with a Strong Acid
2. Strong Base titrated with a Strong Acid
4. Titration of a Strong Base with a Weak Acid
Applications of Acid-Base titrations:

The determination of the concentration of acid in foods and pharmaceuticals.
The measurement of acid number (or base number) during the course of a reaction. For example,
in the production of polyester resins by the reaction of a glycol with maleic and phthalic acids, the
total acid remaining is determined by titration of a weighed sample with potassium hydroxide
using phenolphthalein as indicator.
The Kjeldahl method for nitrogen determination is a good example of a back titration.
1.2 Equivalence Point in Acid-Base Titrations
When a strong base is added to a strong acid, there is a point at which the number of moles of
acid and base are equal, the equivalence point.
moles acid = moles of base
or mmloes acid = mmoles base
x (Macid V acid) = y (Mbase V base)
The equivalence point (EP) for such a titration is usually determined by using an indicator which
changes color near the EP.
Titration Curves may be linear-segment curve or a sigmoidal curve depending on what is plotted
on the y-axis.
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The X-axis units are always reagent or titrant volume.

The Y-axis may be in increments of analyte reacted or product formed (linear-segment curve) or
a p-function such as pH (s-curve).
pH
volume of titrant (mL)

A sigmoidal curve
volume of titrant (mL)

A linear Segment curve
1.3 Titration of Strong Acid with a Strong Base
In the case of a strong acid versus a strong base titration, both the titrant and the analyte (titrand)
are completely ionized. An example would be the determination of HCl concentration by titration
with NaOH.
Na+ OH- + H+ Cl- Na+ Cl- + H2O
The H+ and OH- combine to form H2O and the other ions remain unchanged, so the net result is
conversion of the HCl to a neutral solution of NaCl. The moles of the titrant and the analyte can be
computed as follows:
moles = CNaOH VNaOH = CHClVHCl
The calculation of titration curves simply involves computation of the pH from the concentration of
the particular species present at various stages of titration as outlined in the following sections.
Stage 1: Before Addition of the titrant
The H3O+ ion concentration in the titration medium has two sources:
a. From the H2O solvent (autoionization of water)
b. From the ionization of acid solute - usually this is in great excess relative contribution
from water because the Kw is so small.
The pH of the solution is determined from the hydrogen ion concentration coming from the
complete dissociation of the analyte.
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Stage 2: During the addition of the titrant but before the equivalence point
We calculate the pH of the titration medium from the concentration of unreacted strong acid:
Stage 3: At the equivalence point
All of the acid has reacted with the titrant base. For a strong acid titrated with a strong base, the
salt is a strong electrolyte and therefore completely dissociated. It does not react with H 2O. The
resulting solution is neutral (pH = 7.00) because: HCl + NaOH <=> H2O + Na+ + ClStage 4: After the equivalence point
We calculate the pH of the titration medium from the concentration of unreacted strong base:
Summary
Table 2.1: Key Equations Governing Strong Acid (HX) versus Strong base Titration (BOH)
Stage
Fraction F Titrated
Species Present
Equation
F=0
HX
[H+] = [HX]
0<F< 1
HX/ X-
[H+] = [remaining HX]
F=1
X-
[H+] = Kw
F>1
OH- /X-
[OH-] = [excess titrant]
Table 2.2: Key Equations Governing Strong base Titration (BOH) versus Strong Acid (HX)
Stage
Fraction F Titrated
Species Present
Equation
F=0
BOH
[OH-] = [BOH]
0<F< 1
BOH/B+
[OH-] = [remaining BOH]
F=1
B+
[H+] = Kw
F>1
H+/B+
[H+ ] = [excess titrant]
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EXERCISE
Calculate the pH at 0, 10, 90, 100 and 110% titration for the titration of 50.0 mL of 0.100 M HCl with
0.100 M NaOH.
1.4 Titration of Weak Acid with a Strong Base

Stage 1: Before the addition of strong base:
The H3O+ ion concentration can be calculated from the concentration and Ka of the weak acid.
Stage 2: After the addition of strong base but before the equivalence point:
As soon as the titration is started, some weak acid is converted to its salt, and a buffer system is
set up. As the titration proceeds, the pH slowly increases as the ratio [conjugate base] / [weak
acid] changes. The pH of the solution is calculated as follows:
At the midpoint of titration, [conjugate base] = [weak acid], the pH is equal to the pKa. The
volume of the titrant (strong base) needed to reach the midpoint of the titration can be
determined as follows:
Where,
Vb : volume of titrant
Ve: volume of titrant needed to reach the equivalence point
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Stage 3. At the Equivalence point:
At the equivalence point, we have a solution of the salt. Since this is a Bronsted base (it
hydrolyzes) and the predominant equilibrium is the hydrolysis of the salt of the weak acid:
A- + H2O <=> HA + OH-
Generally, you can solve the equilibrium constant equation for [OH-] and assume that
Thus,
For weak acids that are titrated with strong bases, the pH at the equivalence point will be basic.
The pH will depend on the concentration of the conjugate base. The greater the concentration the
higher the pH.
Stage 4. Beyond the Equivalence point:
- As excess strong base is added beyond the equivalence point, the ionization of the conjugate
base suppressed (Le Chatelier's Principle) to a negligible amount, and the pH is determined only by
the concentration of excess OH-. Therefore, the titration curve beyond the equivalence point
follows for the titration of a strong acid. The hydroxide ion concentration can be calculated as:
Summary
Table 2.3: Key Equations Governing Weak Acid (HA) versus Strong Base Titration (B)
Stage
Fraction F Titrated
Species Present
Equation
F=0
HA
[H+] = Ka CHA
0<F< 1
HA/ A-
F=1
A-
F>1
OH- /A-
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pH = pKa +
[OH-] =
[OH-] = [excess titrant]

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4
Table 2.4: Equations Governing Weak Base Titration (B) versus Strong Acid (HA)
Stage
Fraction F Titrated
Species Present
F=0
0<F< 1
B/BH+
F=1
BH+
F>1
H+/BH+
Equation
[OH-] =
[H+] =
[H+ ] = [excess titrant]
1.5 Important Parameters to Consider during Acid Base titration:

1. The Effect of Reagent Concentration
The more concentrated the solution of analyte

and titrant, the steeper the slope at the
equivalence point region, and a wider choice of
indicators is available to give a sharp end point.
The concentration of indicator must be

minimized to avoid introduction of systematic
error. Adding too much of the indicator will lead
to an indicator error.
2. The Effect of Reaction Completeness
The pH change in the equivalence point

region becomes smaller as the acid becomes
weaker, that is, as the reaction between the
acid and base becomes less complete.
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1.6 Locating End Points using Acid-Base Indicators
The point at which the reaction is observed to be complete is called the endpoint. A
measurement is chosen such that the endpoint coincides with or is very close to the equivalence
point. Hence, one should select an indicator which changes color at the pH at the equivalence
point of the titration.
An indicator is added to the solution to detect visually a color change. An indicator for an
acid-base titration is a weak acid or weak base that is highly colored. Generally, the color of the
ionized form is markedly different from its non-ionized form.
The useful range for a pH indicator is: pH = pKa 1. This means that most indicators require a
transition range of about two pH units. In selecting the indicator for an acid base titration, choose
an indicator with a pKa near the equivalence point pH.
Indicators for Titration of a Strong Acid with Strong Base: Methyl red, bromthymol blue,
phenolphthalein
Indicators for Titration of a Weak Acid with a Strong Base
Weak acid titration: pHequiv > 7.00 therefore, phenolphthalein
Weak base titration: pHequiv < 7.00 therefore, Methyl red or methyl orange
The amount of the indicator present should be kept minimal but sufficient so that it will not
contribute appreciably to the pH and so that only a small amount of titrant will be required to
cause the color change.
1.7 Locating End Points Using pH electrode

An alternative approach to finding a titrations end point is to monitor the
titration reaction with a pH electrode whose signal changes as a function of the analytes
concentration. The resulting titration curve is called a potentiometric titration curve.
The simplest method for finding the end point is to visually locate the inflection point of the
titration curve. However, this is the least accurate method particularly if the titration curves
slope at the equivalence point is small.
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Locating End Points Using First and Second Derivative Plots
The slope of a titration curve reaches its maximum value at the inflection point. The first derivative
of a titration curve, therefore, shows a separate peak for each end point. The first derivative is
approximated as pH/V, where pH is the change in pH between successive additions of
titrant.
The second derivative of a titration curve may be more useful than the first derivative, since the
end point is indicated by its intersection with the volume axis. The second
derivative is approximated as (pH/V)/ V, or 2 pH/V 2.
Derivative methods are particularly well suited for locating end points in multiprotic and multi
component systems, in which the use of separate visual indicators for each end point is impractical.
The precision with which the end point may be located also makes derivative methods attractive for
the analysis of samples with poorly defined normal titration curves.
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1.8 APPLICATIONS OF NEUTRALIZATION TITRATIONS
1. ANALYSIS OF ORGANIC NITROGEN: KJELDAHL ANALYSIS (1883)
An accurate method for determining nitrogen in proteins and nitrogen containing organic
substances.
This method continues to be used in the analysis of caffeine and saccharin in pharmaceutical
products, as well as for the analysis of proteins, fertilizers, sludges, and sediments. Any nitrogen
present in the 3 oxidation state is quantitatively oxidized to NH4+ .
Certain aromatic heterocyclic compounds such as pyridine (C 6H5N) and its derivatives are
particularly resistant t complete decomposition by sulfuric acid.
Kjeldahl's method cannot be used for the organic compounds:

Containing nitrogen in the ring, e.g., pyridine, quinoline etc.
Containing nitro (-NO2) and diazo (-N = N-) groups.
Gravimetric Factors:
% N = 6.25 % protein
fish and meat products

dairy products
cereals, flour, feeds
The Kjeldahl Process:

1. Digestion
- The sample is decomposed and dissolved in boiling concentrated sulfuric acid.
H2SO4
CaHbNc
catalyst
aCO2
1/2 H 2O
cNH 4HSO4
- Carbon and hydrogen converted to CO2 and H2O

- Amides and Amines converted to NH4+ ions
- Azo, azoxy nitro group converted to N or its oxide
Catalysts:
Potassium Sulfate (K2SO4) increases the boiling point of H2SO4

Mercuric Oxide (HgO) increases the rate of reaction and ensures that oxidation is complete.
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2. Distillation
- The digested solution (black color) is cooled and made basic with the addition of NaOH liberating
OHNH3:
2-
cNH 4HSO4
cNH 3
cSO4
The NH3(g) is steam distilled into a receiver containing a known amount of HCl : NH3 + HCl NH4Cl +
HCl.
3. Titration
The excess HCl is back titrated using standard NaOH solution: HCl + NaOH H2O + NaCl
Note:
In some cases NH3 is collected in a boric acid solution : NH3 + H3BO3 NH4+ + H2BO32 The borate excess borate is then titrated with a strong acid: H2BO32- + H3O+ H2BO3 + H2O
EXERCISES
1. A 0.200-g sample containing urea (FM 60.05) is analyzed by the Kjeldahl method. The ammonia is
collected in 50.0 mL of 0.05000 M H2SO4, and the excess acid is back titrated with 0.0500 M NaOH a
procedure requiring 3.40 mL. Calculate the percent urea in the sample. The reactions involved are:
H2SO4 + NaOH Na2SO4 + 2H2O and
2 NH3 + H2SO4 (NH4)2SO4
2. A 0.7121-g sample of wheat flour was analyzed by the kjeldhal method. The ammonia formed by
addition of concentrated base after digestion with H2SO4 was distilled into 25.0 mL of 0.04977 M
HCl. The excess HCl was then back titrated with 3.97 mL of 0.04012 M NaOH. Calculate the percent
protein in the flour.
3. A typical protein contains 16.2 wt % nitrogen. A 0.500-mL aliquot of protein solution was digested
and the liberated NH3 was distilled into 10.00 mL of 0.02140 M HCl. Unreacted HCl required 3.26 mL
of 0.0198 M NaOH for complete titration . Find the concentration of protein (mg protein/mL) in the
original sample. [Answer 25.8 mg protein/mL]
4. The amount of protein in a sample of cheese is determined by a Kjeldahl
analysis for nitrogen. After digesting a 0.9814-g sample of cheese, the nitrogen is oxidized to
NH4+ , converted to NH3 with NaOH, and distilled into a collection flask containing
50.00 mL of 0.1047 M HCl. The excess HCl is then back titrated with 0.1183 M NaOH,
requiring 22.84 mL to reach the bromothymol blue end point. Report the %w/w
protein in the cheese given that there is 6.38 g of protein for every gram of
nitrogen in most dairy products. [Answer 23.1 % w/w protein]
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2) DOUBLE INDICATOR METHOD: ANALYSIS OF CARBONATE MIXTURES
In a solution containing sodium carbonate, sodium hydrogen carbonate, and sodium hydroxide.
No more than two of these three constituents can exist in appreciable amount in any solution.
The analysis of such mixtures requires two titrations, one with an alkaline-range indicator, the
other with an acid-range indicator.
The composition of the solution can then be deduced from the relative volumes of acid needed
to titrate equal volumes of the sample.
The Titration of Sodium Carbonate:
Consider the Neutralization of sodium carbonate:
Inflection Points:
pH = 9 half neutralized
pH = 4 complete neutralization
It is obvious from the molar relationships (look at the reactions involved) of these two equations
that if certain volume of the acid is required to convert a given weight of Na 2CO3 into NaHCO3, an
additional equal volume of the same acid will be required to complete the reaction.
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One application of the double indicator method of titration is in the analysis of carbonate
mixtures.
Consider a Na2CO3 and NaOH mixture

-
The titration with standard acid, using a phenolphthalein, would give a color change from pink to
colorless only when NaOH had been neutralized and Na 2CO3 has been half-neutralized.
Methyl orange would give a yellow color to the solution, and an additional volume of acid required
to change the color to pink would be that to complete the reaction with NaHCO 3. In this case the
additional volume of the acid for the methyl orange endpoint is less that the volume required for
the phenolphthalein endpoint
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Consider a Na2CO3 and NaHCO3 mixture
-
The titration with standard acid using phenolphthalein would produce a color change of pink to
colorless when Na2CO3 had been converted to NaHCO3.
Methyl orange would give a yellow color to the solution, and an additional volume of acid required
to change the color of the methyl orange would be that required to complete the reaction with the
NaHCO3 formed from the Na2CO3 plus that required to react with the original NaHCO 3.
In this case, the additional volume of the acid required for the methyl orange endpoint is greater
than the volume required for the phenolphthalein end point.
Cases Involving mixtures of NaOH and NaHCO 3 are not encountered in practice, since in the
presence of moisture these two compounds are incompatible:
NaOH + NaHCO3 Na2CO3 + H2O
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EXERCISES
1. A 1.200 g sample of a mixture of NaOH and Na 2CO3 containing inert impurities is dissolved and
titrated with cold 0.5000 M HCl. With Phenolphthalein as indicator, the solution turns colorless after
the addition of 30.00 mL of the acid. Methyl Orange is then added, and 5.00 mL more of the acid is
required before this this indicator changes color. What is the percentage of NaOH and of Na 2CO3 in
the sample? [Answer: % NaOH = 41.67% ; %Na2CO3 = 22.08%]
2. A 1.200 g sample of an impure mixture of Na 2CO3 and NaHCO3 containing only inert impurities is
dissolved and titrated with cold 0.5000 M HCl. With phenolphthalein indicator, the solution turns
colorless after the addition of 15.00 mL of the acid. Methyl orange is then added, and 22.00 mL
more of the acid is required to change the color of this indicator. What is the percentage of Na 2CO3
and of NaHCO3 in the sample. [Answer % Na2CO3 = 66.25% ; %NaHCO3 = 24.50%]
3. A 0.500 g sample containing NaHCO3 and Na2CO3, and H2O was dissolved and diluted to 250.0 mL. A
25.0 mL aliquot was boiled to remove with 50.0 mL of 0.01255 M HCl. After cooling, the excess acid
in the solution required 2.34 mL of 0.01063 M NaOH when titrated to the phenolphthalein
endpoint. A second 25.00 mL aliquot was then treated with excess of BaCl 2 and 25.00 mL of the
base. All the carbonate precipitated and 7.63 mL of the HCl was required to titrate the excess
base. Determine the composition of the mixture. [Answer: Na2CO3 = 45.85%, NaHCO3 = 28.56%,
H2O = 25.59]
4. A series of solutions containing NaOH, Na 2CO3, and NaHCO3, alone or in compatible combination,
was titrated with 0.1202 M HCl. Tabulated below are the volumes of the acid need to titrate 25.00
mL portions of each solution to (1) phenolpthalein and (2) bromocresol green endpoint. Use this
information to deduce the composition of the solutions. In addition, calculate the number of
milligrams of each solute per milliliter (mg/mL) of solution.
(1) Phenolphthalein End Point
(2) Bromocresol Green End Point
(a)
22.42
22.44
(b)
15.67
42.13
(c)
29.64
36.42
(d)
16.12
32.23
(e)
0.00
33.33
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3) CHARACTERIZATION APPLICATIONS
- Neutralization titrations are often used to determine the EQUIVALET MASS of purified organic acids.
Equivalent masses serve as an aid in the qualitative identification of organic acids.
-
In this method, an accurately weighed sample of a pure acid or base is titrated to a well-defined
equivalence point using a monoprotic strong acid or strong base. If we assume that the titration
involves the transfer of n protons, then the moles of titrant needed to reach the equivalence point
is given as:
Moles titrant = n x moles analyte
and the formula weight is
Since the actual number of protons transferred between the analyte and
titrant is uncertain, we define the analytes equivalent weight (EW) as the apparent formula
weight when n = 1. The true formula weight, therefore, is an integer multiple of the calculated
equivalent weight.
FW = n (EW)
Thus, if we titrate a monoprotic weak acid with a strong base, the EW and FW are identical. If the
weak acid is diprotic, however, and we titrate to its second equivalence point, the FW will be twice
as large as the EW.
ILLUSTRATIVE EXAMPLE
A 0.2521-g sample of an unknown weak acid is titrated with a 0.1005 M
solution of NaOH, requiring 42.68 mL to reach the phenolphthalein end point. Determine the
compounds equivalent
unknown weak acid?
ascorbic acid
malonic acid
succinic acid
citric acid
L.LAPITAN JR.2013
weight.
Which of the following compounds is most likely to be the
C6H8O6 FW = 176.1
C3H4O4 FW = 104.1
C4H6O4 FW = 118.1
C6H8O7 FW = 192.1
monoprotic
diprotic
diprotic
triprotic

OF ANALYSIS
4
Solution:
The moles of NaOH needed to reach the end point is :
MbVb = 0.1005M x 0.04268L = 4.289 x 103 mol NaOH.
This gives an equivalent weight of:
EW = (g analyte/mole titrant) = (0.2521g/4.289x10-3mol) = 58.78 g/mol
The possible formula weights for the unknown weak acid are
for n = 1:
FW = 1 x EW = 58.78 g/mol
for n = 2:
for n = 3:
FW = 2 x EW = 117.6 g/mol
FW = 3 x EW = 176.3 g/mol
If the weak acid is monoprotic, then the FW must be 58.78 g/mol, eliminating ascorbic acid as a
possibility. If the weak acid is diprotic, then the FW may be either 58.78 g/mol or 117.6 g/mol,
depending on whether the titration was to the first or second equivalence point. Succinic acid, with a
formula weight of 118.1 g/mol is a possibility, but malonic acid is not. If the analyte is a triprotic
weak acid, then its FW must be 58.78 g/mol, 117.6 g/mol, or 176.3 g/mol. None of these values is close
to the formula weight for citric acid, eliminating it as a possibility. Only succinic acid provides a possible
match.
EXERCISES
1. A 250.0-mg sample of an organic weak acid was dissolved in an appropriate solvent and titrated
with 0.0556 M NaOH, requiring 32.58 mL to reach the end point. Determine the compounds
equivalent weight. [Answer: 138 g/equivalent]
2. A dilute solution of an unknown weak acid required a 28.62 mL titration of 0.1084 M NaOH to
reach a phenolphthalein endpoint. The titrated solution was evaporated into dryness . Calculate
the equivalent mass of the acid if the sodium salt was found to weigh 0.2110 g. [Answer: 46.03
gHA/mol]
3. Weight of sample = 0.2245 g, Standardization: 31.75 mL NaOH required 35.11 mL of 0.1056 N
HCl ; Volume of std. NaOH used for titration = 30.00 mL. Detremine the identity of the weak acid
from the given data.
(A) Oxalic acid, H2C2O4 (FM = 90); (B)Potassium Acid Phtalate, KHC8H4O4 (FM = 204.2); (C) Citric
Acid, H3(C6H5O7) (FM = 192)
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4) INORGANIC ANALYSIS USING DEVRADAs ALLOY
- Inorganic analytes that are neutral in aqueous solutions may still be analyzed if they can be
converted to an acid or base. For example, NO 3 can be quantitatively analyzed by reducing it to NH3
in a strongly alkaline solution using Devardas alloy, a mixture of 50% w/w Cu, 45% w/w Al, and 5%
w/w Zn.
3NO3 (aq) + 8Al (s) + 5OH (aq) + 2H 2 O(l) 8AlO2 (aq) + 3NH3 (aq)
-
The NH3 is removed by distillation and titrated with HCl.
EXERCISE
1. A 1.291 sample containing (NH4)2SO4, NH4NO3, and nonreactive substances was diluted to 200.0
mL in a volumetric flask. A 25.00 mL aliquot was then made basic, and the liberated ammonia was
distilled into 30.00 mL of 0.08421M HCl. After this reaction was complete, the excess
HCl was titrated with 10.17 mL of 0.08802M NaOH. A 25.00 mL aliquot of the sample was then
obtained, made basic, and the NO3 - was reduced to NH3 with Devardas alloy. The NH3 from both
ammonium ion and nitrate ion was then distilled into 30.00 mL of the standard acid and back
titrated with 14.16mL of the base. Calculate the percent (NH4)2SO4 and NH4NO3 present in the
sample. [Answer: (NH4)2SO4 = 15.23% ; NH4NO3 =24.39%]
2. A 1.291 sample containing (NH4)2SO4, NH4NO3, and inert material was diluted to 250.0 mL in a
volumetric flask. A 50.00 mL aliquot was then made basic, and the liberated ammonia was
distilled into 30.00 mL of 0.08421M HCl. After this reaction was complete, the excess
HCl was titrated with 10.17 mL of 0.08802M NaOH. A 25.00 mL aliquot of the sample was then
obtained, made basic, and the NO 3 - was reduced to NH3 with Devardas alloy. This aliquot was
then distilled into 30.00 mL of the standard acid. It required 14.16 mL of the standard base to
react with the excess acid from the second distillation. Calculate the percent (NH 4)2SO4 and
NH4NO3 present in the sample. [Answer: (NH4)2SO4 = 18.0% ; NH4NO3 = 28.8% %]
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5) OTHER APPLICATIONS OF NEUTRALIZATION TITRATIONS:
Selected Elemental Analysis based on Neutralization Titration
Element
Liberated
Determined
as
Reactions producing Acid or base titrated
Titration
NH3 (g)
NH3(g) + H3O + (aq) NH4 +(aq) + H2O(l)
excess H3O+ with strong

base
SO2 (g)
SO2 (g) + H2O2(aq) H2SO4(aq) + H2SO4
H2SO4 with strong base
CO2
CO2(g) + Ba(OH)2(aq) BaCO3(s) + H2O(l)
excess Ba(OH)2 with strong

acid
Cl
HCl(g)
HCl(g) + H2O(l) H3O+ (aq) + Cl (aq)
H3O+ with strong base
SiF4 (g)
3SiF4(g) + 2H2O(l) 2H2 SiF6(aq) + SiO2(s)
H2SiF6 with strong
Selected Neutralization Procedures for the determination of Organic Functional Groups

Functional
Group
Ester
Carbonyl
Alcohol
Reaction Involved
RCOOR(aq) + OH(aq) RCOO (aq) + HOR(aq)
excess OH with strong acid
Aldehydes
and
Ketones
react
with HCI with strong base
hydroxylamine hydrochloride. The reaction
produces an oxime and HCl. The liberated HCl is
then titrated with a standard base:
R2C=O + NH2OH.HCl R2C=NOH +HCl +H2O
[1] The acetylation reaction is carried out in
pyridine to avoid the hydrolysis of acetic
anhydride by water:
(CH3CO)2O + ROH CH3COOR + CH3COOH
CH3COOH with strong base; ROH is

determined from the difference in the
amount of titrant needed to react
with a blank consisting only of acetic
anhydride, and the amount reacting
[2] After the acetylation is complete, water is with the sample.
added to convert the remaining acetic
anhydride to acetic acid.
(CH3CO)2O + H2O 2CH3COOH
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EXERCISES
1. The active ingredient in Antabuse, a drug for the treatment of chronic alcoholism, is
teraethylthiuram disulfide (296.54 g/mol):
S
(C2H5)2 -N- C-S-S-C-N-(C2H5)2

The sulfur in a 0.4169-g sample of an Antabuse preparation was oxidized to SO 2 which was
absorbed in H2O2 to give H2SO4. The acid was titrated with 19.25 mL of 0.04216 M base. Calculate
the percentage of active ingredient in the sample. [Answer: 7.216%].
2. A 3.00 L of urban air was bubbled through a solution containing 50.0 mL og 0.0116 M Ba(OH) 2,
which caused the CO2 in the sample to precipitate as BaCO3. The excess base was back titrated to a
phenolphthalein endpoint with 23.6 mL of 0.0108 M HCl. Calculate the concentration of CO2 in the
air in parts per million (that is mL CO2/106 mL air); use 1.98 g/L for the density of CO 2.[Answer: 3.35
x 103 ppm].
3. The concentration of SO2 in atmospheric samples can be determined by bubbling a sample of air
through a trap containing H2O2. Oxidation of SO2 by H2O2 results in the formation of H2SO4, the
amount of which can be determined by titrating with NaOH. In a typical analysis, a sample of air
was passed through the peroxide trap at a rate of 1.25 L/min for 60 min and required 10.08 mL of
0.0244 M NaOH to reach the phenolphthalein end point. Calculate the parts per million of SO 2
(mL/L) in the sample of air. The density of SO 2 at the temperature of the air sample is 2.86 mg/mL.
[Answer: 36.7 ppm SO2]
4. The purity of a synthetic preparation of methylethyl ketone (C 4H8O) can be determined by reacting
the ketone with hydroxylamine hydrochloride, liberating HCl. In a typical analysis, a 3.00-mL sample
was diluted to 50.00 mL and treated with an excess of hydroxylamine hydrochloride. The liberated
HCl was titrated with 0.9989 M NaOH, requiring 32.68 mL to reach the end point. Report the
percent purity of the sample, given that the density of methylethylketone is 0.805 g/mL. [Answer:
97.47%]
5. Animal fats and vegetable oils are triacylglycerols, or triesters, formed from the reaction of glycerol
(1, 2, 3-propanetriol) with three long-chain fatty acids. One of the methods used to characterize a
fat or an oil is a determination of its saponification number. When treated with boiling aqueous
KOH, an ester is saponified into the parent alcohol and fatty acids (as carboxylate ions). The
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4
saponification number is the number of milligrams of KOH required to saponify 1.000 g of the fat or
oil. In a typical analysis, a 2.085-g sample of butter is added to 25.00 mL of 0.5131 M KOH. After
saponification is complete, the excess KOH is back titrated with 10.26 mL of 0.5000 M HCl. What is
the saponification number for this sample of butter? [Answer: 207]
6. A 0.9471 g sample containing dimethylpthalate, C6H4(COOCH3)2 (194.19 g.mol), and unreactive
species where refluxed with 50.00 mL of 0.1215 M naOH to hydrolyze the ester groups (this process
is called saponification): C6H4(COOCH3)2 + 2OH- C6H4(COO)2 2- + 2CH3OH
After the reaction was complete, the excess NaOH was back titrated with 24.27 mL of 0.1644 M
HCl. Calculate the percentage of dimethylphthalate in the sample. [Answer: 21.38%]
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TOPIC 2 - ASSESSMENT
solutions for items requiring computations on the spaces provided for each number. Erasures will
invalidate your answer.
____1. In a solution containing only a weak monoprotic acid HA, [H 3O+] is ____ [A-]; if the solution is
not very dilute, the concentration of nonionized HA is approximately equal to the ____ of the solution.
A. equal to, molarity
B. greater than, molarity
C. less than, molarity
D. equal to, pH
____ 2. Calculate the pH of a solution of acetic acid that is 3.0% ionized. Ka for acetic acid = 1.8 X 10-5
A. 2.64
B. 3.24
C. 2.94
D. 4.99
____ 3. Trimethylamine ionizes as follows in water. What concentration of trimethylammonium ion,
(CH3)3NH+, is present in 9.0 10-2 M (CH3)3N? Kb for trimethylamine = 7.4 10-5
(CH3)3N + H2O
A. 1.6 x10-4 M
B. 5.2x 10-3 M
C. 3.8 x10-4 M
D. 2.6x10-3 M
(CH3)3NH+ + OH-
____ 4. Calculate the pH of 0.050 M benzoic acid (Ka for Benzoic acid = 6.3
A. 4.20
B. 1.45
C. 5.50
D. 2.75
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4
____ 5. Calculate the acid ionization constant of an unknown monoprotic weak acid, HA, if its salt, NaA,
has a (base) hydrolysis constant of 6.2 10-9.
A. 6.0x 10-7
B. 1.6 x 10-6
C. 4.5 x 10-7
D. 5.6 x 10-8
____ 6. Calculate the [H3O+] in 0.030 M potassium fluoride, KF (Ka for HF= 7.2
A. 2.5 x 10-8 M
10-4).
B. 1.5 x 10-8 M
C. 8.3 x10-9 M
D. 6.8 x 10-4 M
____ 7. What is the pH of a solution which is 0.0400 M in formic acid, HCO2H (K a for formic acid = 1.8
10-4), and 0.0600 M in sodium formate, NaHCOO?
A.
B.
C.
D.
3.92
3.96
4.00
9.52
____ 8. If 0.040 moles of solid NaOH is added to 1.0 liter of a solution that is 0.10 M in NH3 (Kb for
ammonia = 1.8 10-5 ) and 0.20 M in NH4Cl, what will be the pH of the resulting solution? Assume no
volume change due to the addition of the NaOH.
A. 4.80
B. 8.95
C. 5.05
D. 8.65
____ 9. Consider a buffer consisting of 0.75 M NH3 and 0.50 M NH4Cl. If 0.10 M H2SO4 is added to the
solution with no change in volume, what is the resulting pH?
A. 4.56
B. 9.44
C. 9.29
D. 9.16
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____ 10. If 400. mL of 0.100 M CH3COOH (Ka for acetic acid = 1.8 10-5) and 200. mL of 0.100 M
NaCH3COO solutions are mixed, what is the pH of the resulting solution?
A. 3.09
B. 3.33
C. 3.78
D. 4.44
____ 11. Calculate the ratio [CH3COOH]/[NaCH3COO] that gives a solution with pH = 5.00.
[CH3COOH]/[NaCH3COO] ____.
A.
B.
C.
D.
0.28
0.36
0.44
0.56
____ 12. How many grams of KNO2 must be added to 5.00 liters of 0.67 M HNO2 (Ka for nitrous = 4.5
10-4) solution to produce a buffer with pH = 3.15? Assume no change in volume.
A. 181 g
B. 3.15 g
C. 270 g
D. 53.6 g
____ 13. How much NH4Cl must be added to 2.00 liters of 0.200 M aqueous ammonia to give a solution
with pH = 8.20? Assume no volume change due to the addition of NH 4Cl. (Kb for NH3 = 1.8 10-5 )
A. 246 g
B. 166 g
C. 2.25 g
D. 123 g
____ 14. Calculate the pH of a solution prepared by adding 115 mL of 0.100 M NaOH to 100. mL of
0.100 M HNO3 solution.
A. 11.60
B. 11.68
C. 11.76
D. 11.84
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____ 15. What is the [H3O+] in a solution resulting from mixing of 100. mL of 0.100 M HCN (Ka for
hydrocyanic acid = 4.0 10-10) and 10.0 mL of 0.100 M KOH?
A. 9.1 x 10-3 M
B. 5.7 x 10-6 M
C. 3.6 x 10-9 M
D. 8.2 x 10-5 M
1) A 0.9092-g sample f wheat flour was analyzed by the Kejdahl procedure. The ammonia formed
was distilled into 50.00 mL of 0.02532 M H2SO4. A 7.46 mL back-titration with 0.04917 M NaOH
was required. Calculate the %N (FM -14.00) in the sample and the percent protein in the sample.
2) Consider a mixture that may contain either pure NaOH (FM 39.997), pure Na 2CO3 (FM 105.989)
and pure NaHCO3 (FM 84.007) or compatible combination of these bases along with inert
materials. A sample weighing 4.017 g was dissolved in 500.0 mL water. Titration of the 50.00 mL
sample requires 14.42 mL of 0.1052 M HCl to reach the phenolphthalein endpoint, and an
additional 26.58 mL was used to reach the methyl orange endpoint. Determine the identity of the
active component(s), and calculate the percentage (of each) present in the original mixture.
Express your final answer in four (4) significant figures.
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TOPIC 3
PRECIPITATION TITRATIONS
- A reaction in which the analyte and titrant form an insoluble precipitate also can form the basis for a
titration. We call this type of titration a precipitation titration.
- The importance of precipitation titrimetry as an analytical method were developed for determining
Ag + and halide ions. Titrations with silver nitrate are sometimes called argentometric titrations.
- The titration curve for a precipitation titration follows the change in either the analytes or titrants
concentration as a function of the volume of titrant. The titration curve may be a plot of pAg or pI
as a function of the titrants volume
EXERCISE
Calculate the pAg of the solution during the titration of 50.00 mL of 0.0500 M NaCl with 0.1000 M
AgNO after the addition of the following volumes of reagent:
(a) 0.00 mL, (b) 24.50 mL,
(c) 25.00 mL, (d) 25.50 mL.
3.2 The Shapes of Titration Curves

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A) Effect of titrant concentration on precipitation
titration curves.
Note the increased sharpness of the break for

the more concentrated solution, A
Curve A shows 50.00 mL of 0.0500 M NaCl with 0.1000 M
AgNO3,
Curve B shows 50.00 mL of 0.00500 M NaCl with 0.01000 M
AgNO3 .
B) Effect of reaction completeness on precipitation

titration curves.
Note that smaller values of Ksp give much

sharper breaks at the end point.
For each curve, 50.00 mL of a 0.0500 M solution of the anion
was titrated with 0.1000 M AgNO3
3.3 Precipitation Titrations: Indicators

Three types of end points are encountered in titrations with silver nitrate: (1) chemical, (2)
potentiometric, and (3) amperometric.
3.4 Chemical Indicators for Argentometric Titrations

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1. The Mohr Method: Formation of a Colored Precipitate.
The high chromate ion concentration imparts such an intense yellow color to the solution.
Lower concentrations of chromate ion are generally used, and, as a consequence, excess silver nitrate
is required before precipitation begins. An additional excess of the reagent must also be added to
produce enough silver chromate to be seen (Use Blank titration in actual analysis!).
The Mohr titration must be carried out at a pH of 7 to 10 because chromate ion is the conjugate base
of the weak chromic acid. Consequently, in acidic solutions, where the pH is less than 7, the
chromate ion concentration is too low to produce the precipitate.
2. The Fajans Method: Adsorption Indicators
-
Common adsorption indicators are anionic dyes, which are attracted to positively charged particles
produced immediately after the equivalence point.
Adsorption of the negatively charged dye onto the positively charged surface changes the color of
the dye. Fluorescein is a typical adsorption indicator
Before Equivalence Point: In the early stages of the titration of chloride ion with silver nitrate,
the colloidal silver chloride particles are negatively charged because of adsorption of excess
chloride ions. The dye anions are repelled from this surface by electrostatic repulsion.
AgCl:Cl-::Na+
Beyond the equivalence point, the silver chloride particles strongly adsorb silver ions and
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thereby acquire a positive charge. Fluoresceinate anions are now attracted into the counter-ion
layer.
AgCl: Ag+::In
The net result is the appearance of the red color of silver fluoresceinate in the surface layer of
the solution surrounding the solid.
3. The Volhard Method: Forming a Colored Complex
This is an indirect titration procedure for determining anions that precipitate with silver (Cl -, Br-,SCN-)
and it is performed in acidic (HNO3)solution.
An measured excess of AgNO3 is used to precipitate than anion and then determine the excess Ag+
by back-titration with standard potassium thiocyanate solution.
X- + Ag+ AgX(s) + excess Ag+
excess Ag+ + SCN- AgSCN(s)
The endpoint is detected by adding iron (II) as a ferric ammonium sulfate) , which forms a soluble
red complex with the first excess titrant:

Fe3+ + SCN- Fe(SCN)2+
- If the precipitate, AgX, is less soluble than AgSCN, we do not have to remove the precipitate before
titrating.
- If the precipitate , AgX, is more soluble than AgSCN, it will react with the titrant to give a high and
diffuse end point. Such is the case with AgCl:
AgCl + SCN- AgSCN(s) + ClTherefore, we remove the precipitate by filtration before titrating.
3.5 Volumetric Technique: Blank Titration

In Blank determinations, all steps for the analysis are performed in the absence of the sample.
Blank determinations reveal errors due to interfering contaminants from vessels or reagents
employed in analysis
Blanks also allow the analyst to correct titration data for the volume of reagent needed to cause
an indicator to change color at an endpoint
EXERCISES
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1. A Fajans Titration of a 0.7908 g sample of required 45.32 mL of 0.1046 M AgNO3. Express the
results of this analysis in terms of the percentage
(a) Cl(b) BaCl2.H2O
(c) ZnCl2.2NH4Cl (234.28 g/mol)
2. To an aqueous solution containing solution of a 1.6000 g sample consisting of a mixture of
CaBr2H2O (FW = 308.0) and inert matter is added 52.00 mL of 0.200 M AgNO 3. The excess Ag+
requires 4.0 mL of 0.1000 M KCNS for the precipitation of AgCNS. What is the percentages of Br
and of inert matter in the sample?
3. A 0.5131-g sample containing KBr is dissolved in 50 mL of distilled water. Titrating with 0.04614 M
AgNO3 requires 25.13 mL to reach the Mohr end point. A blank titration requires 0.65 mL to reach
the same end point. Report the %w/w KBr in the sample.
4. 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 and NaBr in the sample.
5. A 0. 200-g sample of impure Na2CO3 was analyzed by the Volhard method. After adding 50.00 mL
of 0.0700 M AgNO3, the sample was back titrated with 0.0600 M KSCN, requiring 27.36 mL to
reach the end point. Calculate the %w/w Na 2CO3 sample.
6. A 2.414 g sample containing KCl, K2SO4, and inert materials was dissolved in sufficient water to
give 250.00 mL of solution. A Mohr Titration of the 50.00 mL aliquot required 41.36 mL of 0.05818
M AgNO3. A second 50.00 mL aliquot was treated with 40.00 mL of 0.1083 mL M NaB(C 6H5)4. The
reaction is:
NaB(C6H5)4 + K+ KB(C6H5)4 (s) + Na+
The solid was filtered, redissolved in acetone and titrated with 49.98 mL of the AgNO 3 solution
according to the reaction: KB(C6H5)4 + Ag+ AgB(C6H5)4(s) + K+
Calculate the percentage of KCl and K2SO4 in the sample.
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TOPIC 3 ASSESMENT
____1. Which statement about solubility product constant, Ksp , is false?
A. It is a constant at a given temperature.
B. It equals the equilibrium constant in equilibria that involve slightly soluble compounds in water.
C. The concentration of the solid is not included in the solubility product expression.
D. The solubility product expression is the product of the concentrations of the compound's constituent
ions.
____2. A lab technician adds 0.015 mol of KOH to 1.00 L of 0.0010 M Ca(NO3)2. Ksp = 6.5 10
Ca(OH)2 . Which of the following statements is correct?
A) Calcium hydroxide precipitates until the solution is saturated.
B) The solution is unsaturated and no precipitate forms.
C) The concentration of calcium ions is reduced by the addition of the hydroxide ions.
D) One must know K sp for calcium nitrate to make meaningful predictions on this system.
-6
for
____ 3. The Ksp for Zn3(AsO4)2 is 1.1 10-27. When 100 mL of 5.5 10-4 M Zn2+ is mixed with 50 mL of
1.2 10-4 M AsO43-, which of the following statements is true?
A. A precipitate forms, because Qsp > Ksp.
C. No precipitate forms, because Qsp > Ksp.
B.A precipitate forms, because Qsp < Ksp.
D. No precipitate forms, because Qsp < Ksp.
____4. Which of the following has the lowest molar solubility in water at 25C?
A. Ni(CN)2, Ksp = 3.0 10-23 B. ZnS, Ksp = 1.1 10-21 C. PbS, Ksp = 8.4 10-28 D.Co3(AsO4)2, Ksp = 7.6
10-29
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____5. Calculate the pH of a saturated aqueous solution of Co(OH) 2. Ksp is 2.5 10-16.
A. 8.60
B. 8.90
C. 9.10
D. 9.20
____6. How many grams of MgF2 will dissolve in 150. mL of 0.100 M NaF solution? Ksp for MgF2 = 6.4
10-9
A. 6.2 10-7 g
B. 4.1 10-6 g
C. 1.0 10-5 g
D. 6.0 10-6 g
____7. Calculate the [Ca2+] required to start the precipitation of calcium fluoride, CaF 2, from a solution
containing 0.0025 M F- at 25C. Ksp for CaF2 = 3.9 10-11.
A. 6.4 10-7 M
B. 5.2 10-10 M
C. 4.8 10-3 M
D. 6.2 10-6
M
____8. A solution contains 0.025 M Ba2+. If 9.7 g of Na2CO3 is added to 1.0 L of this solution, what
percentage of Ba2+ remains in solution? Assume no change in volume occurs. Ksp(BaCO3) = 8.1 10-9.
A. 27.3 %
B. 6.6 %
C. 0.00049 %
D. 0.000012 %
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____ 9. An industrial plant processes its waste water through a sedimentation tank that removes
hazardous metals by precipitating them as insoluble carbonate salts. If sodium carbonate is gradually
added to the tank, what would be the order of precipitation of the metals, Pb 2+, Cu2+, Hg22+, and Zn2+ if
each is 1.0 104 M? (Ksp PbCO3 = 7.4 1014, Ksp CuCO3 = 1.4 1010, Ksp Hg2CO3 = 8.9 1017, and
Ksp ZnCO3 = 1.4 1011)
A) Pb2+, Hg22+, Zn2+, Cu2+
C) Cu2+, Zn2+, Pb2+, Hg22+
B) Hg22+, Pb2+, Zn2+, Cu2+
D) Cu2+, Zn2+, Hg22+, Pb2+
____ 10. Consider the titration of 20.0 mL of 0.150 M NaBr with 0.100 M AgNO3. What is the pAg at the
start of the titration, when the first tiny crystal of AgBr is formed. The Ksp of AgBr = 5.25 x 10-13.
A. 11.460
B. 11.104
C. 10.99
D. Indeterminate
____ 11. What is the pAg when 10.00 mL of AgNO 3 is added in the titration of Problem 10 ?
A. 11.460
B. 11.104
C. 10.99
D. Indeterminate
____ 12. What is the pAg when 40.00 mL of AgNO 3 is added in the titration of problem 10?
A. 6.140
B. 1.778
C. 2.453
D. 1.569
____ 13. A 10.00 mL aliquot of the chloride solution is treated with 15.00 mL standard 0.1182 M AgNO 3
solution. The excess silver is titrated with standard 0.1010 M KCNS solution, requiring 2.38 mL to reach
the endpoint. Calculate the molar concentration of chloride.
A. 0.0153
B. 0.0172
C. 0.172
D. 0.153
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____ 14. A 0.500-g sample containing BaBr2 (FM = 297.14) is dissolved in 50 mL of distilled water.
Titrating with 0.0400 M AgNO3 requires 25.00 mL to reach the Mohr end point. A blank titration
requires 0.50 mL to reach the same end point. Calculate the %w/w BaBr2 in the sample
A. 28.17
B.59.43
C. 29.12
D.58.24
____ 15. A 0. 200-g sample of impure Na2CO3 (FM =106) was analyzed by the Volhard method. After
adding 50.00 mL of 0.0700 M AgNO3, the sample was back titrated with 0.0600 M KSCN, requiring
27.36 mL to reach the end point. Calculate the %w/w Na2CO3 sample.
A. 98.50
B. 49.25
C. 32.83
D. 24.62
1.
The formaldehyde (CH2O) in a 5.00 g sample of a seed disinfectant was steam distilled, and the
aqueous distillate was collected in a 500.0 mL volumetric flask. After dilution to volume, a 25.0 mL
aliquot was treated with 30.0 mL of 0.121 M KCN solution to convert formaldehyde to potassium
cyanohydrins:
K+ + CH2O + CN - KOCH2CN
The excess KCN was then removed by addition of 40.0 mL of 0.100 M AgNO 3:
2CN- + 2 Ag+ Ag2(CN)2
+
The excess Ag in the filtrate and washings required 16.1 mL titration with 0.134 M NH 4SCN:
Ag+ + SCN- AgSCN(s)
Calculate the percent CH2O (FM = 32) in the sample.
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TOPIC 4
COMPLEX - FORMATION TITRATIONS
-
A titration in which the reaction between the analyte and titrant is a Complexation reaction.
The utility of complexation titrations improved following the introduction by Schwarzenbach, in
1945, of aminocarboxylic acids as multidentate ligands capable of forming stable 1:1
complexes with metal ions. The most widely used of these new ligands was
ethylenediaminetetraacetic acid, EDTA, which forms strong 1:1 complexes with many
metal ions.
As titrants, multidentate ligands, particularly those having four or six donor groups, have two
advantages over their unidentate counterparts. First, they generally react more completely with
cations and thus provide sharper end. Second, they ordinarily react with metal ions in a single-step
process (leads to a sharp equiv point regions)
4.1 Titration curves for Complexometric Titrations

Titration of 60.0 mL of a solution that is 0.020 M
in M with:
(curve A) a 0.020-M solution of
the tetradentate ligand D to give MD as the
product;
(curve B) a 0.040-M solution of
the bidentate ligand B to give MB2 ; and
(curve C) a 0.080- M solution of
the unidentate ligand A to give MA4 .
The overall formation constant for each product is 1020.
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4.2 EDTA Titrations
EDTA, is the most widely used complexometric titrant.
EDTA is a hexadentate ligand.

Disodium salt of EDTA (Na2H2Y)is used as a titrant
The various EDTA species are often abbreviated HY, HY, HY, HY, and Y.
4.3 The Nature of EDTA Complexes with Metal Ions
Solutions of EDTA are particularly valuable as titrants because the reagent combines with metal
ions in a 1 : 1 ratio regardless of the charge on the cation.
4.4 Structure of a metal/EDTA complex

EDTA behaves here as a hexadentate ligand in
that six donor atoms are involved in bonding the
divalent metal cation.
- Hydrogen ions are liberated during the titration of
metal ions with disodium EDTA:
Mg2+ + H2Y2- MgY2- + 2H+
Al3+ + H2Y2- AlY- + 2H+
Th4+ + H2Y2- ThY + 2H+
- Because of the liberation of hydrogen ions, the

solution is buffered and so prevents large change in
pH during titration.
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4.5 The Nature of EDTA Complexes with Metal Ions
formation constants KMY
The alpha value for free EDTA is:
where cT is the total molar concentration of uncomplexed EDTA
To obtain the conditional formation constant for the equilibrium, we substitute 4cT for [Y4-] in
the formation constant expression:
Combine the two constants 4 and KMY to yield the conditional formation constant KMY:
Computing 4 Values for EDTA Solutions
where K , K , K , and K are the four dissociation
constants for HY and D is the denominator
of the equation.
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4.6 EDTA Titration Curves
EXERCISES
Calculate the pCa during the titration of 50.0 mL of 0.00500 M Ca2+ with 0.0100 M EDTA
solution that is buffered at a constant pH of 10.00 after the addition of
(a) 5.00
(b) 25.00
(c) 26.00 mL of the titrant.
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4.7 Factors Influencing EDTA Titrations
A) Influence of pH on the titration of 0.0100 M
Ca2+ with 0.0100 M EDTA.
The end point becomes less sharp as the
pH decreases because the
complex-formation reaction is less
complete under these circumstances.
B) Minimum pH needed for satisfactory

titration of various cations with EDTA.
(From C. N. Reilley and R. W. Schmid, Anal.
Chem., 1958, 30, 947. With permission of
the American Chemical Society.)
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4.8 Indicators for EDTA Titrations
- Most indicators for Complexation titrations are organic dyes that form stable complexes with
metal ions. These dyes are known as metallochromic indicators.
- To function as an indicator for an EDTA titration, the metalindicator complex must
possess a color different from that of the uncomplexed indicator. Furthermore, the formation
constant for the metalindicator complex must be less favorable than that for
the metalEDTA complex
- Eriochrome Black T is a typical metal-ion indicator
- The metal complexes of Eriochrome Black T are generally red-purple. it is necessary to adjust
the pH to 7 or above so that the blue form of the species, HIn, predominates
EXERCISE
1. The concentration of a solution of EDTA was determined by standardizing against
a solution of Ca2+ prepared from the primary standard CaCO 3. 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. A 50.00-mL portion of this
solution was transferred into a 250-mL Erlenmeyer flask and the pH adjusted by adding 5 mL of a
pH 10 NH3 NH 4Cl buffer containing a small amount of Mg2+EDTA. After adding
calmagite
as
requiring
titrant.
42.63
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visual
mL
to
indicator,
reach
the
the solution
was
titrated
with
the
EDTA,
end point. Report the molar concentration of the


OF ANALYSIS
4
4.9 Titration Methods Employing EDTA
1. Direct Titration
- Analyte is titrated with standard EDTA
-
Analyte is buffered to a pH at which the conditional formation constant for the metal-EDTA
complex is large and the color of the indicator is distinctly different from that of the
metal-indicator complex
2. Back-Titration Methods
A measured excess of standard EDTA solution is
added to the analyte solution.
The excess EDTA is back-titrated with a standard magnesium or zinc ion solution to an
Eriochrome Black T or Calmagite end point.
Back titration is necessary:
- If the analyte precipitates in the absence of EDTA
- If the analyte reacts slowly with EDTA
- If the analyte blocks the indicator
3. Displacement Methods
where M represents the analyte cation. The liberated Mg or, in some cases Zn, is then
titrated with a standard EDTA solution
Displacement titrations are used when no indicator for an analyte is available.
4. Masking
A masking agent is a reagent that protects some component of the analyte from reaction with
EDTA.
Example: Al3+ in the mixture of Mg2+ and Al3+ can be
thereby leaving only the Mg2+ to react with EDTA.
measured by first masking the Al 3+ with F-
Demasking releases the metal ion from the masking agent.
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A.
Masking is achieved by the following:

pH control: some interferences can be removed
by
lowering the pH of the solution to a
point where the reaction with EDTA is negligible eg. titration of Fe 3+ (with
high formation constant) is possible without interference from Ca2+ (low stability constant) at
low pH.
B.
Precipitation: the interferent can be removed by precipitation eg. Precipitation of

magnesium as the hydroxide at pH 12 leaves only the calcium for titration. Problems of
coprecipitation may occur .
C.
Change in oxidation state: many metals behave differently in different oxidation

states eg. complexes of EDTA with Fe (II) are significantly less stable than iron (III) so masking of
iron interferences could be achieved by reducing the iron (III) to iron (II) with ascorbic acid and
lowering the pH.
D.
Complexation: use of another complexing agent in the reaction, which forms a more stable
complex with the interferent than does EDTA. This prevents the interfering species reacting with
EDTA.
EXERCISES
1. Calamine, which is used for relief of skin irritations, is a mixture of zinc and iron oxides. A 1.022-g sample
of dried calamine was dissolved in acid and diluted to 250.0 mL . Potassium fluoride was added to a 10.0
mL aliquot of the diluted solution to mask the iron; after suitable adjustment of the pH, Zn 2+ consumed
38.71 mL of 0.01294 M EDTA. A second 50.00 mL aliquot was suitably buffered and titrated with 2.40 mL of
0.002727 M ZnY2- solution: Fe3+ + ZnY2- FeY- + Zn2+. Calculate the % wt. of ZnO (FM = 81.41) and The %
wt. of Fe2O3 (FM = 159.69). [Answer: 99.7 % and 0.256%]
2. A 0.60004-g sample of Ni/Cu condenser tubing was dissolved in acid and diluted to 100.0 mL in a
volumetric flask. Titration of both cations in a 25.00 mL aliquot of this solution required 45.81
mL of 0.05285 M EDTA. Mercaptoacetic acid and NH3 were then introduced; production of the
Cu complex with the former resulted in the release of an equivalent amount of EDTA, which
required 22.85 mL titration with 0.07238 M Mg2+. Calculate the percentages of Cu (At. Mass =
63.55) and Ni (At. Mass = 58.69) in the alloy.
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3. An alloy of chromel containing Ni, Fe, and Cr was analyzed by a complexation
titration using EDTA as the titrant. A 0.7176 - g sample of the alloy was
dissolved in HNO3 and diluted to 250 mL in a volumetric flask. A 50.00-mL aliquot of the
sample, treated with pyrophosphate to mask the Fe and
Cr, required 26.14 mL of
0.05831 M EDTA to reach the murexide end point. A second 50.00-mL aliquot was
treated with hexamethylenetetramine to mask the Cr. Titrating with 0.05831 M EDTA required
35.43 mL to reach the murexide end point. Finally, a third 50.00-mL aliquot was
treated with 50.00 mL of 0.05831 M EDTA, and back titrated to the murexide end point with 6.21
mL of 0.06316 M Cu2+ . Report the weight percents of Ni, Fe, and Cr in the alloy.
4. A mixture of Mn2+, Mg2+, and Zn2+ was analyzed as follows: The 25.00-mL sample was treated with
0.25 g of NH3OH+Cl- (hydroxylammonium chloride, a reducing agent that maintains manganese in
the +2 state), 10 mL of NH3-NH4Cl buffer (pH 10), and a few drops of Eriochrome Black T indicator
and then diluted to 100.0 mL. It was warmed to 40C and titrated with 39.98 mL of 0.04500 M
EDTA to the blue end point. Then 2.5 g of NaF was added to displace Mg 2+ from its EDTA complex.
The liberated EDTA required 10. 26 mL of standard 0.02065 M Mn 2+ for complete titration. After
this second end point was reached, 5 mL of 15 wt % aqueous KCN was added to displace Zn2+ from
its EDTA complex. This time the liberated EDTA required 15.47 mL of standard 0.02065 M Mn 2+.
Calculate the number of milligrams of each metal Mn 2+, Zn2+, and Mg2+) in the 25.00-mL sample of
unknown.
4.10 APPLICATIONS OF EDTA TITRATIONS

Water Hardness
- Hardness is the total concentration of akaline earth (GII-A) ions which are mainly Ca2+ and Mg2+
ions in water.
- Water hardness is commonly expressed as equivalent number of milligrams of CaCO 3 per liter
(ppm CaCO3).
-
Temporary Water Hardness the fraction hardness due to Ca(HCO3)2 (aq) because this calcium is
lost (by precipitating CaCO3) upon heating : CaCO3(s) +CO2 + H2O Ca(HCO3)2(aq)
Permanent Water Hardness hardness arising from other salts ( mainly dissolved CaSO4)
because it is not removed by heating.
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EXERCISES
1. A standard solution of EDTA is prepared and by titration each mL is found to complex with the Mg
in 10.00 mL of a solution containing 0.300 g MgCl 2 per liter. A 100.0 mL pipetful of a certain well
water is found to require 8.60 mL of the standard EDTA. With the knowledge that the conventional
method of expressing water hardness in terms of ppm of CaCO 3 regardless of the nature of the
cations and anions actually present, what is the hardness of the well water?
2. Titration of Ca2+ and Mg2+ in a 50.00 mL sample of hard water required 23.65 mL of 0.01205 M
EDTA. A second 50.0 mL aliquot was made strongly basic with NaOH to precipitate Mg 2+ as
Mg(OH)2(s). The supernatant liquid was titrated with 14.53 mL of the EDTA solution. Calculate the
concentration CaCO3 (FM = 100.09) in the sample as in ppm and calculate ppm MgCO3 (FM = 84.314)
[Answer: 350. 5 ppm and 185.3 ppm]
The Liebig Titration
The earliest titrimetric applications involving metalligand complexation were the

determinations of cyanide and chloride using, respectively, Ag+ and Hg2+ as titrants. Both
methods were developed by Justus Liebig (18031873) in the 1850s.
Used for the determination of cyanide
The titration is carried out by the slow addition of AgNO 3 in a solution of a cyanide forming a
soluble cyanide complex of silver:
2CN-1 + Ag+ Ag(CN)2-1
The endpoint of the titration is the formation of a permanent faint turbidity:
Ag(CN)2-1 + Ag+ Ag[Ag(CN)2](s)
EXERCISES
1) In the Liebig Titration, calculate % NaCN (FW=49.02) in a 0.500-g sample of raw material, after the
addition of 15.23 mL of 0.0866 M AgNO3 to reach the equivalence point.
2) Before the introduction of EDTA most Complexation titrations used Ag + or CN as the titrant. The
analysis for Cd2+, for example, was accomplished indirectly by adding an excess of KCN to form
Cd(CN)42 , and back titrating the excess CN with Ag+ , forming Ag(CN)2-. In one such analysis, a
0.3000-g sample of an ore was dissolved and treated with 20.00 mL of 0.5000 M KCN. The excess
CN required 13.98 mL of 0.1518 M AgNO3 to reach the end point. Determine the %w/w Cd in the
ore.
L.LAPITAN JR.2013

OF ANALYSIS
4
TOPIC 4 - ASSESMENT
solutions for items requiring computations on the spaces provided for each number. Erasures will invalidate
your answer.
_____1. What would be the stable structure of the complex hexacyanoferrate(II), Fe(CN)64(A) linear
(B) octahedral
(C) tetrahedral
(D) square planar
_____2. How many ethylenediamine (en) molecules are present in a Cu(en) 2+ complex with a CN of 4?
(A) Four
(B) Five
(C) Three
(D) Two
_____3. Which of the following statements is NOT TRUE about EDTA?
(A) It forms a stable and stoichiometric ligand with metal ions
(B) In EDTA titrimetry, selectivity, among various cations may be obtained by controlling the pH of the
solution
(C) EDTA forms very strong complexes with Group I metal cations than Group II and III ions
(D) The fully deprotonated form contains 6 donor groups capable of forming covalent bonds with a
metal ion.
____4. The reaction of EDTA with a divalent metal ion, such as Cu 2+, complexed with ammonia could be
represented as
(A) M(NH3)42++ Y4MY2- + 4NH3.
(C) M(NH4)46+ + Y4MY2- + 4NH44+.
2+
426+
4(B) M(NH3) + Y
MY + NH3
.(D) M(NH4)2 + Y
MY2- + 2NH44+.
____5. Which of the following EDTA titrations would be most complete?
(A) Cu2+ at pH 10
(B) Al3+ at pH 4
(C) Fe3+ at pH 5
(D) Mg2+ at pH 3.0
____6. When is a direct EDTA titration not useful?

(A) When the metal precipitates in the absence of EDTA.
(C) When the metal does not block the
indicator.
(B) When the metal reacts too quickly with EDTA.
(D) none of the above
____7. Which of the following displacement titrations would be feasible?
(A) Ag+ + MgY2Mg2+ + AgY3(C) Cu2+ + MgY22+
22+
2(B) Ba + MgY
Mg + BaY
(D) Ca2+ + MgY2-
Mg2+ + CuY2Mg2+ + CaY2-
____8. Calculate the pCo2+ after 14.00 mL of 0.03846 M EDTA in the titration of 25.00 mL of 0.020 M
Co2+ (Kf = 2.04 X 1016) at pH = 6.00.
(A) 10.455
(B) 15.196
(C) 3.51 x 10-11 molar
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OF ANALYSIS
4
Co2+ (Kf = 2.04 x 1016) at pH = 6.00.
(A) 9.095
(B) 6.723
(C) 1.89 x 10-7 molar
Co2+ (Kf = 2.04 x 1016) at pH = 6.00.
(A) 1.04 x 10-3 molar
(B) 4.415
(C) 2.983
____11. The Thalium (Tl, FM = 204.38) in a 9.57-g sample of rodenticide was oxidized to the trivalent
state and treated with unmeasured excess of Mg/EDTA solution. The reaction is: Tl 3+ + MgY2- TlY- +
Mg2+
Titration of the liberated Mg2+ required 12.77 mL of 0.03160 M EDTA. Caculate the percentage Tl 2SO4
(FM = 504.8) in the sample.
(A) 1.06%
(B) 12.2 %
(C) 2.43%
(D) 24.3 %
____12. A 50.0 mL aliquot of a solution containing iron(II) and iron (III) required 10.98 mL of 0.01500M
EDTA when titrated at a pH 2.0 and 23.70 mL of the same EDTA solution when titrated at pH 6.0.
Express the concentration the Fe2+ and Fe3+ in parts per million (ppm)
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OF ANALYSIS
4
(A) 92 ppm Fe2+ and 107 ppm Fe3+
(B) 107 ppm Fe2+ and 92 ppm Fe2+
(C) 184 ppm Fe2+ and 213 ppm Fe3+
(C) 213 ppm Fe2+ and 184 ppm Fe3+
____13. An EDTA solution was prepared by dissolving approximately 4 g of the disodium salt in
approximately 1 L of water. An average of 42.35 mL of this solution was required to titrate 50.0 mL
aliquots of a standard that contained 0.7682 g of MgCO 3 per liter (FM MgCO3= 84.314). Titration of a
25.0 mL sample of mineral water at pH 10 required 18.81 mL of the EDTA solution. A 50.00 mL aliquot
of the mineral water was rendered strongly alkaline to precipitate Mg(OH)2. Titration with calcium
specific indicator required 31.54 mL of the EDTA solution. Calculate the molarity of EDTA solution.
(A) 0. 0998 M
(B) 0.0200 M
(C) 0.10178 M
(D) 0.01076 M
____14. Calculate the ppm CaCO3 in the mineral water

(A) 55.15
(B) 339. 6 ppm
(C) 679. 2 ppm
(D) 110.3 ppm
____15. Calculate the ppm MgCO3 in the mineral water

(A) 55.15 ppm
(B) 339.6 ppm
(C) 679.2 ppm
(D) 110.3 ppm
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4
TOPIC 5
REDUCTION OXIDATION (REDOX) TITRATIONS
1.1 General Principles of REDOX titrations
1. The analyte to be titrated must be in definite oxidation state. Sometimes this necessitates some
kind of preliminary chemical treatment.
2. The REDOX reaction that occurs during titration must be quantitative.
3. For direct titration, the oxidation reaction must be quite fast since some oxidation reactions occur
fairly or very slow.
For slow redox reactionsindirect titration must be done.
Indirect Titration a measured excess of the standard oxidizing solution is added to the sample,
and sufficient time is allowed for the reaction to be complete. The excess of the oxidizing chemical
is back-titrated by a standard reducing solution that reacts rapidly with the oxidant.
4. There must be a good way to detect the end point.
Use of visible indicator (i.e. color change)
Use of Potentiometric method (common)
5.2 Preadjustment of Oxidation State
If a redox titration is to be used in a quantitative analysis, the analyte must initially be present in
a single oxidation state.
This type of pretreatment can be accomplished with an auxiliary reducing or oxidizing agent.
For Example: The iron content of a sample can be determined by a redox titration in which Ce 4+
oxidizes Fe 2+ to Fe 3+ . The process of preparing the sample for analysis must ensure that all
iron is present as Fe2+. However, the iron may initially be present in both the +2 and +3
oxidation states. Before titrating, any Fe 3+ that is present must be reduced to Fe 2+.
A) Auxillary Reducing Agents

Metals that are easily oxidized, such as Zn, Al, and Ag, can serve as auxiliary reducing agents.
The metal, as a coiled wire or powder, is placed directly in the solution where it reduces the
analyte.
The residual auxiliary reducing agent, therefore, must be removed once the analyte is
completely reduced. This can be accomplished by simply removing the coiled wire or by
filtering.
An alternative approach to using an auxiliary reducing agent is to immobilize it in a column.

To prepare a reduction column, an aqueous slurry of the finely divided metal is packed in a glass
L.LAPITAN JR.2013

OF ANALYSIS
4
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 analytes
complete reduction.
The Jones Reductor

The column is filled with amalgamated Zn prepared by briefly placing Zn granules in a solution of
HgCl2 to form Zn(Hg)(s).
Oxidation of the amalgamated Zn provides the electrons for reducing the analyte:
Zn(Hg)(s) Zn2+ (aq) + Hg (l) + 2e
The Walden Reductor
The column is filled with granular Ag metal.
The solution containing the analyte is acidified with HCl and passed through the column where
the oxidation of Ag provides the necessary electrons for reducing the analyte:
Ag(s) + Cl (aq) AgCl (s) + e
B) Auxillary Oxidizing Agents
Ammonium Peroxydisulfate, (NH4)2S2O8 ,
Ammonium peroxydisulfate is a powerful oxidizing agent capable of oxidizing Mn 2+ to MnO4 ,
Cr3+ to Cr2O72 , and Ce 3+ to Ce4+
S 2O82 (aq) + 2e 2SO42 (aq)
Excess peroxydisulfate is easily destroyed by briefly boiling the solution.
Hydrogen Peroxide: H2O2
The reduction of hydrogen peroxide in acidic solution provides another
oxidizing an analyte.
H2O2 (aq) + 2H3O+(aq) + 2e 4H2O(l)
Excess H2O2 also can be destroyed by briefly boiling the solution.
L.LAPITAN JR.2013
method for

OF ANALYSIS
4
Sodium Bismuthate, NaBiO3
Sodium bismuthate is a powerful oxidizing agent; it is capable, for example, of converting
manganese(II)
quantitatively to permanganate ion.
The half-reaction for the reduction of sodium bismuthate can be written as:
NaBiO3(s) + 4H+ + 2e- BiO+ + Na+ + 2H2O
5.3 Constructing REDOX Titration Curves
For a redox titration, it is convenient to monitor the volume of the titrant (x-axis) versus the
electrochemical potential (y - axis).
Consider a titration in which the analyte in a reduced state, A red ,is titrated with a titrant in an
oxidized state, Tox . The titration reaction is:
A red + T ox
T red + A ox
1) Before Equivalence Point
The titration mixture consists of appreciable quantities of both the oxidized and reduced forms
of the analyte, but very little unreacted titrant. The potential, therefore, is best calculated using
the Nernst equation for the analytes half-reaction:
2) At Equivalence Point
We cannot calculate the potential at the equivalence point, Eeq, using just the Nernst equation
for the analytes half-reaction or the titrants half-reaction individually.
However, we can calculate Eeq by combining the two Nernst equations
3) After Equivalence Point
After the equivalence point, the potential is easiest to calculate using the Nernst equation
for the titrants half-reaction, since significant quantities of its oxidized and
reduced forms are present.
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OF ANALYSIS
4
EXERCISES
Consider the titration of 50.0 mL of 0.100 M iron(II) with standard 0.100 M cerium(IV) in 1 M
HClO4:
Ce4+
Ceric
titrant
Reduction reaction :
Reduction reaction :
Fe2+
Ferrous
analyte
Ce4+ + e- Ce 3+
Fe3+ + e- Fe 2+
Ce 3+
Cerous
Fe 3+
Ferric
Eo= 1.70 V
Eo = 0.767 V
The equilibrium constant for the reaction is quite large (it is approximately 6 x
1015 ), so we may assume that the analyte and titrant react completely . Calculate how the cell voltage
changes as Fe2+is titrated with Ce4+ at the following volumes of the titrant added:
(a) 0.00 mL
(b) 5.00 mL
(c) 25.00 mL
(d) 50.00 mL
(e) 60.00 mL
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OF ANALYSIS
4
5.4 Effect of Variables on Redox Titration Curves
Reactant Concentration
titration curves for oxidation/reduction reactions are usually independent of analyte and
reagent concentrations.
Completeness of the Reaction
The change in the equivalence-point region of an oxidation/reduction titration becomes
larger as the reaction becomes more complete.
The effect of titrant electrode potential on

reaction completeness. The standard
electrode potential for the analyte is 0.200 V;
starting with curve A, standard electrode
potentials for the titrant are 1.20, 1.00, 0.80,
0.60, and 0.40, respectively. Both analyte
and titrant undergo a one electron change.
5.5 General Redox Indicators
A redox indicator is a compound that changes color when it goes from its oxidized to its reduced
state.
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OF ANALYSIS
4
-
The potential change required to produce the full color change of a typical general indicator
a typical general indicator exhibits a detectable color change when a titrant causes the system
potential to shift from
to
or about (0.118/n)
V.
5.6 Specific REDOX Indicators

The best-known specific indicator is starch, which forms a dark blue complex with triiodide ion.
This complex signals the end point in titrations in which iodine is either produced or consumed.
Small molecules can fit into the center of the coiled, helical polymer. In the presence of starch,
iodine forms I6 chains inside the amylose helix and the color turns dark blue
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OF ANALYSIS
4
5.7 Reagents Used in REDOX Titrations
A) Reducing agents
Ferrous salts :
ammonium iron(II) sulfate hexahydrate (Mohrs salt): FeSO 4(NH4)2SO46H2O

iron(II) ethylene diamine sulfate (Oespers salt): FeC 2H4(NH3)2(SO4)24H2O
Sodium thiosulfate pentahydrate : Na2S2O35H2O
Arsenic trioxide: arsenious oxide
As2O3
Sodium oxalate and oxalic acid dihydarte : Na 2(COO)2 , (COOH)22H2O
Potassium ferrocyanide: K4Fe(CN)6 3H2O
Sodium Thiosulfate, Na2S2O3
Thiosulfate ion is a moderately strong reducing agent that has been widely used to determine
oxidizing agents by an indirect procedure that involves iodine as an intermediate.
With iodine, thiosulfate ion is oxidized quantitatively to tetrathionate ion according to the
half-reaction:
2S2O3 2
S4O6 2 + 2e
Standardization of thiosulfate solutions

Solutions of Na2S2O3 are prepared from the
standardized before use.
Eo = 0.08
pentahydrate
and
must be
Standardization is accomplished by dissolving a carefully weighed portion of the

primary standard KIO3 in an acidic solution containing an excess of KI.
When acidified, the reaction between IO 3 and I Titration reactions:
IO3 (aq) + 8I (aq) + 6H3O+(aq) 3I3 (aq) + 9H2O(l)

I3- (aq) + 2S2O3 2 (aq) 3I- (aq) + S4O62 (aq)
Stability of Na2S2O3 Solutions
Thiosulfate is one of the few reducing titrants not readily oxidized by contact with air,
However, it is subject to a slow decomposition to bisulfite and elemental
sulfur.
Na2S2O3 + H2O + CO2 Na2CO3 + H2S2O3

H2S2O3 H2SO3 + S
Several forms of bacteria are able to metabolize thiosulfate, which also
a change in its concentration. This problem
preservative such as HgI2 to the solution.
L.LAPITAN JR.2013
can
be
can lead
to
minimized by adding a

OF ANALYSIS
4
Ferrous ammonium sulfate, Fe(NH4)(SO 4 )2.6 H2O Solutions

Iron is present in the +2 oxidation state.
Solutions of Fe2+ are normally very susceptible to air oxidation, but when prepared in 0.5 M
H2SO4 the solution may remain stable for as long as a month.

Periodic restandardization with K2Cr2O7 is advisable:
Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ +6 Fe3+ + 7H2O
B) Oxidizing agents
Potassium permanganate KMnO4
Ceric sulfate / Ceric ammonium sulfate Ce(SO 4)22(NH4)2SO44H2O

Potassium dichromate K2Cr2O7 : Dichrometry
Iodine
I2 : Iodimetry, Iodometry
Potassium iodate KIO3: Iodometry
Potassium bromated: KBrO3
1. Permanganimetry
KMnO4 is a powerful oxidant that the most widely used.
In strongly acidic solutions (1M H2SO4 or HCl, pH 1)
violet color
colorless manganous
KMnO4 is a self-indicator.
In feely acidic, neutral, or alkaline solutions
MnO4 + 4H+ + 3e- = MnO2 (s) + 2H2 O
Eo = 1.695 V
brown manganese dioxide solid
Solutions of MnO 4 are prepared from KMnO4 , which is not available as a primary standard.
Aqueous solutions of permanganate are thermodynamically unstable due to its ability to oxidize
water.
4MnO4 (aq) + 2H2O(l) 4MnO2 (s) + 3O 2 (g) + 4OH (aq)
This reaction is catalyzed by the presence of MnO2 , Mn + , heat, light, and the presence of
acids and bases.
Moderately stable solutions of permanganate can be prepared by boiling for an
hour and filtering through a sintered glass filter to remove any solid
precipitates.
Moderately stable
L.LAPITAN JR.2013
solutions of permanganate
can
MnO 2 that
be prepared by boiling for an

OF ANALYSIS
4
hour and filtering through a sintered glass filter to remove any solid MnO 2 that
precipitates. Solutions prepared in this fashion are stable for 12 weeks,
although the standardization should be rechecked periodically.
Standardization of KMnO4 solution
- Potassium permanganate is not primary standard, because traces of MnO 2 are invariably
present.
- Standardization may be accomplished using the same primary standard reducing agents
that are used with Ce4+ , using the pink color of MnO 4 to signal the end
point.
Primary Standards:
1. Sodium oxalate : C2O4-2 2 CO2 + 2 e2. Arsenic Oxide: As3+ + 4 H2O H3AsO4 + 5 H+ + 2e3. Ferrous Solutions: Fe2+ Fe3+ + e2. Cerimetry: Titration with Cerium (IV)
yellow
colorless
1.61 V in 1 M HNO3
1.47 V in 1 M HCl
Indicator : ferroin, diphenylamine

Primary Standard: Sodium oxalate.
Analytically Useful Cerium (IV) Compounds: (Expensive!!!!!!)
Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, and Ce(HSO4)4, (NH4)4Ce(SO4)42H2O
3. Dichromate Process
-
Potassium dichromate is a relatively strong oxidizing agent whose principal advantages are its
availability as a primary standard and the long-term stability of its solutions. It is not, however,
as strong an oxidizing agent as MnO4 or Ce4+ ,
The half reaction is : Cr2O72 (orange) + 14H+ + 6e- = 2Cr3+ (green) + 7H2O
Eo = 1.36 V
Primary Standard: K2Cr2O7 is a primary standard.
Indicator : diphenylamine sulphonic acid
barium diphenylamine sulfonate
The principal use of dichromate is for the volumetric determination of iron(II):
Cr2O72- + 6 Fe2+ 14H+ 2Cr3+ +6 Fe3+ + 7H2O

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OF ANALYSIS
4
4. Iodometric Titration (Indirect Titration with Iodine)
- In comparison with MnO4, Ce 4+ , and Cr2O72 , it is a weak oxidizing agent and
useful only for the analysis of analytes that are strong reducing agents.
-
is
The reduction half-reaction for I2 is
I2 (aq) + 2e 2I (aq)
-
Because of iodines poor solubility, solutions are prepared by adding an excess of I . The
complexation reaction
I2(aq) + I (aq) I3 (aq)

increases the solubility of I 2 by forming the more soluble triiodide ion, I 3 . Even though iodine
is present as I 3 instead of I 2 , the number of electrons in the reduction half-reaction is unaffected.
Solutions of I3
indicator for I3
are
normally standardized
against Na 2S2O3 using starch as a specific
I3- (aq) + 2S2O3 2 (aq) 3I- (aq) + S4O62 (aq)
Indicator : Starch (as a specific indicator for I3) .

Titration Reaction: 2 S2O3-2 + I2 S4O62- + 2IPrimary Standard: K2Cr2O7 (Cr2O72- + 6I- 6Cr 3+ + 3 I2)
EXERCISES
1. The amount of Fe in a 0.4891-g sample of an ore was determined by a redox titration with K 2Cr
2O7.
The sample was dissolved in HCl and the iron brought into the +2 oxidation state using a
Jones reductor. Titration to the diphenylamine sulfonic acid end point required
36.92 mL of 0.02153 M K2Cr 2O7 . Report the iron content of the ore as %w/w Fe 2O3 .[77.86%
w/w Fe2O3]
2. A 25.00-mL sample of a liquid bleach was diluted to 1000 mL in a volumetric flask. A 25-mL
portion of the diluted sample was transferred by pipet into an Erlenmeyer
flask and
treated
with excess KI, oxidizing the OCl to Cl , and producing

. The liberated I3
was determined by titrating with 0.09892 M Na 2S2O3 , requiring 8.96 mL to reach the
L.LAPITAN JR.2013
I3

OF ANALYSIS
4
starch indicator end point. Report the %w/v NaOCl in the sample of bleach. [Ans. 0.132% w/v
NaOCl]
3. The level of dissolved oxygen in a water sample can be determined by the Winkler method. In a
typical analysis, a 100.0-mL sample is made basic, and treated with a solution of MnSO4, resulting
in the formation of MnO2.
2Mn2+ (aq) + 4 OH (aq) + O2 (aq) 2MnO2 (s) + 2 H2O(l)
An excess of KI is added, and the solution is acidified, resulting in the formation of Mn 2+ and I3- .
MnO2 (s) + 3 I (aq) + 4 H3O+ (aq) Mn2+ (aq) + I3(aq) + 6H2O(l)
The liberated I3- is titrated with a solution of 0.00870 M Na2S2O3, requiring 8.90 mL to reach the
starch indicator end point.
(a) Calculate the mass of dissolved oxygen (FM for O 2 = 32.00 g) in milligram (mg).
(b) Express the concentration of dissolved oxygen in parts per million
4. The amount of ascorbic acid, C 6H8O6 , in orange juice was determined by
oxidizing the ascorbic acid to dehydroascorbic acid, C 6H8O6 , with a known excess
of I3, and back titrating the excess I3 with Na 2 S2O3 . A 5.00-mL sample of filtered orange juice
was treated with 50.00 mL of excess 0.01023 M I 3. After the oxidation was complete,
13.82 mL of 0.07203 M Na2S2O3 was needed to reach the starch indicator end point.
Report the concentration of ascorbic acid in milligrams per 100 mL. [Ans. 48.6 mg/100 mL of
orange juice].
5. A 5.00 mL sample of brandy was diluted to 1.00 L in a volumetric falsk. The ethanol in 25.00 mL
aliquout of the diluted solution was distilled into 50.0 mL of 0.02000 M K2Cr2O7 and oxidized to
acetic acid with heating. 3C2H5OH + 2Cr2O72- + 16 H+ 4 Cr3+ + 3CH3COOH + 11 H2O
After cooling, 20.00 mL of 0.1253 M Fe3+ was pipetted into the flask. The excess Fe2+ was then
titrated with 7.46 mL of standard K2Cr2O7 to a diphenylamine sulfonic acid endpoint. Calculate the
percent (w/v) ethanol (MW 46.07 g/mol) in the brandy.
L.LAPITAN JR.2013

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ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

1.1 Criteria for a Successful Volumetric Analysis

titration error: Et = Vep Veq

Analytical Chemistry Review Notes 1

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

1.3 Standard Solutions

Analytical Chemistry Review Notes 2

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

Analytical Chemistry Review Notes 3

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

1.8 Volumetric Technique: Back Titration

Analytical Chemistry Review Notes 4

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

Analytical Chemistry Review Notes 5

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

4. Consider the following data:

Analytical Chemistry Review Notes 6

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

B. equivalence point error

C. The reaction flask only

B. The pipette and burette only

D. All of the apparatuses

_____5.Which of the following statements are correct?

C. (2) and (3) only

B. (1) and (3) only

D. (1), (2) and (3)

Analytical Chemistry Review Notes 7

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

A) The same pH but one tenth the concentration of HCl.

C) The same pH and same number of

D) A pH that has increased by one.

Final burette reading (mL)

The mean titre is:

_____8. Properties of a primary standard for use in acid-base titrations include...

A) low molar mass and low solubility.

C) reactive with oxygen and low molar mass.

B. Potassium hydrogen phthalate.

C. Oxalic acid. D. Anhydrous sodium

A) They contain carbonate and adsorbed water

C) They have relatively low molecular

B) They have limited solubility in the titration medium

D) They are not readily available at

Analytical Chemistry Review Notes 8

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

The [H3O+] ion concentration equals Ka of the acid

A) To eliminate the reaction product, carbon dioxide and carbonic acid

Analytical Chemistry Review Notes 9

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

4Cr3+(aq) + 3CH3COOH(aq) + 11H2O(l)

What was the molarity of the alcohol in the beer?

B. 0.0613 mol L-1

C. 0.273 mol L-1

D. 0.613 mol L-1

Analytical Chemistry Review Notes 10

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

Analytical Chemistry Review Notes 11

ANALYTICAL CHEMISTRY: VOLUMETRIC METHODS MODULE

There are two end points are observed in the