VOLUMETRIC ANALYSIS / TITRIMETRY

Antonio G. Celajes Jr., RCh

WCC PRAYER
 LAST MEETING’S LEARNING OBJECTIVES
At the end of the lesson, the students will be able to differentiate several methods of quantitative analysis and relate them
in medical technology field.

Introduction to Quantitative Analysis

a. Different Methods of Quantitative Analysis

Gravimetric Method of Analysis

a. Overview and Importance of Gravimetry
a.1 Using Mass as a Signal
a.2 Types of Gravimetric Methods
a.3 Conservation of Mass
a.4 Why Gravimetry Is Important?
 LAST MEETING’S LEARNING OBJECTIVES
b. Volatilization Gravimetry
b.1 Theory and Practice
b.2 Quantitative Applications
b.3 Evaluating Volatilization Gravimetry
c. Precipitation Gravimetry
c.1 Theory and Practice
c.2 Quantitative Applications
c.3 Qualitative Applications
c.4 Evaluating Precipitation Gravimetry
 LAST MEETING’S LEARNING OBJECTIVES
d. Particulate Gravimetry
d.1 Theory and Practice
d.2 Quantitative Applications
d.3 Evaluating Precipitation Gravimetry
 TODAY’S LEARNING OBJECTIVES
At the end of the lesson, the students will be able to judge which titrimetric technique to be used when given a sample of known analyte.
a. Overview of Titrimetry
a.1 Equivalence Points and End Points
a.2 Volume as a Signal
a.3 Titration Curves
a.4 The Buret
b. Titrations Based on Acid–Base Reactions
b.1 Acid–Base Titration Curves
b.2 Selecting and Evaluating the End Point
b.3 Titrations in Non-aqueous Solvents
b.4 Representative Method
b.5 Quantitative Applications
b.6 Qualitative Applications
b.7 Characterization Applications
b.8 Evaluation of Acid–Base Titrimetry
 TODAY’S LEARNING OBJECTIVES
c. Titrations Based on Complexation Reactions
c.1 Chemistry and Properties of EDTA
c.2 Complexometric EDTA Titration Curves
c.3 Selecting and Evaluating the End Point
c.4 Representative Method
c.5 Quantitative Applications
c.6 Evaluation of Complexation Titrimetry
 TODAY’S LEARNING OBJECTIVES
d. Titrations Based on Redox Reactions
d.1 Redox Titration Curves
d.2 Selecting and Evaluating the End Point
d.3 Representative Method
d.4 Quantitative Applications
d.5 Evaluation of Redox Titrimetry
e. Precipitation Titrations
e.1 Titration Curves
e.2 Selecting and Evaluating the End Point
e.3 Quantitative Applications
e.4 Evaluation of Precipitation Titrimetry
 TITRIMETRY
Titrimetry
- refers to that group of analytical techniques which takes advantage of titers or concentrations
of solutions;
- In metallurgy the word "titer" refers to the fineness of gold or silver;
- In chemistry it is the measure of the concentration of a solution;
- In medicine it is defined as the extent to which an antibody solution can be diluted before it
ceases to give a positive reaction with an antigen.
- In titrimetry we add a reagent, called the titrant, to a solution containing another reagent, called
the titrand, and allow them to react;
- Though in chemistry the term titrimetry often refers to the use of some volume of a solution of
known concentration to determine the quantity of analyte, there are still some variations on the
use of the term;
TITRIMETRY
- It is used rather to denote a quantity of some other measurement parameter which relates
directly to the quantity of analyte which is to be measured:

Volumetric titrimetry establishes a quantity of analyte using volumes of reagents of known

concentrations and the knowledge of the stoichiometry of the reactions between the reagents
and the analyte(s);

Gravimetric titrimetry determines the quantity of analyte by a measure of the mass of a solution
of known concentration;

Coulometric titrimetry arrives at the amount of analyte by measuring the duration of a given
electrical current. Since amperes x time = coulombs or total charge, the number of equivalents
of analyte can be measured by relating the extent of reaction to the number of moles of
electrons (Faradays).
 TITRIMETRY
The type of reaction provides us with a simple way to divide titrimetry into the following four
categories:
- acid–base titrations, in which an acidic or basic titrant reacts with a titrand that is a
base or an acid;

- complexometric titrations based on metal–ligand complexation;

- redox titrations, in which the titrant is an oxidizing or reducing agent; and

- precipitation titrations, in which the titrand and titrant form a precipitate.

 TITRIMETRY
Common Features of Titrimetry
Equivalence point is the point at which a volume, a mass or a quantity of charge equivalent to
the amount of analyte present in the sample to be measured is reached. It is the point of
stoichiometric chemical equivalence.

The end point is the point at which some detection technique tells you that chemical
equivalence has been reached. The end point may occur before or after the equivalence point,
giving a titration error. It is for this reason that blank samples are often used. Blank samples are
prepared so that you have a measure of the amount that needs always to be added to or
subtracted from the end point (the titration error) to achieve the equivalence point.
 TITRIMETRY
Common Features of Titrimetry
A titration curve provides us with a visual picture of how a property of the titration
reaction changes as we add the titrant to the titrand.

A buret is a long, narrow tube with graduated markings, equipped with a stopcock for
dispensing the titrant. The buret’s small internal diameter provides a better defined
meniscus, making it easier to read the titrant’s volume precisely.
 TITRIMETRY
In titrations, primary and secondary standards are used:
Standard solutions are referred to either as primary standards or secondary standards. Primary standards can be
prepared by weighing directly and dissolving to a measured volume the reagent which is to react with the analyte.
But primary standards must meet stringent requirements:
1. High purity
2. Stability in presence of air
3. Absence of any water of hydration which might vary with changing humidity and temperature.
4. Cheap
5. Dissolves readily to produce stable solutions in solvent of choice
6. A larger rather than smaller molar mass

These conditions are met by few materials. Anhydrous sodium carbonate, silver nitrate, potassium hydrogen phthalate are a
few which do meet these conditions.
 TITRIMETRY
Criteria for Practical Use of Standard Solutions
So as to be useful as a measure of the quantity of analyte in a sample, a standard solution must meet four criteria:
1. The reagent in the solution must have sufficient stability so that its concentration need be determined only
once. Any deterioration in strength due to reaction with components of water or air would make the reagent
unacceptable.
2. The reagent in the solution must react rapidly with the analyte. Slow approaches to equilibrium can cause
erroneous judgments about reaction completeness.
3. The reaction of the analysis must occur with a completeness easily detectable by an appropriate indicator.
4. The reagent must react with the analyte in a simple and stoichiometrically predictable manner. Any side
reactions would render a reagent unacceptable.

Two excellent standard solutions are those of hydrochloric acid, HCl and potassium hydrogen phthalate, KHC8H4O4. Three
others which have some instability but with appropriate precautions have proven to be excellent standard solutions are
sodium thiosulfate, Na2S2O3 (light sensitivity, susceptible to bacterial oxidation), silver nitrate, AgNO3 (light sensitivity) and
potassium permanganate, KMnO4 (water oxidation catalyzed by light, heat, Mn2+ and MnO2).
 TITRIMETRY
Determination of the concentration of a standard solution.

The direct method of solution standardization is the obvious choice if the reagent is a
primary standard which meets all of the criteria described above and whose weight
offers a repeatable observation proportional to the number of moles of substance
expected. Solutions of sodium carbonate and silver nitrate can be prepared in this
manner.

The method of standardization can be used if a primary standard reacts quantitatively

with the reagent needed in the standard solution. HCl cannot be considered to be a
primary standard because of its gaseous form at room temperature, but its solutions may
be standardized against anhydrous Na2CO3.
 TITRATIONS BASED ON ACID BASE
REACTIONS
-Most acid–base titrations used H2SO4, HCl, or HNO3 as acidic titrants, and K2CO3 or
Na2CO3 as basic titrants;
-A titration’s end point was determined using litmus as an indicator, which is red in acidic solutions
and blue in basic solutions, or by the cessation of CO2 effervescence when neutralizing
carbonate;
-Three limitations slowed the development of acid–base titrimetry: the lack of a strong base
titrant for the analysis of weak acids, the lack of suitable indicators, and the absence of a
theory of acid–base reactivity.

-Titrating Strong Acids and Strong Bases ie HCl vs NaOH

-Titrating a Weak Acid with a Strong Base ie acetic acid vs NaOH
 TITRATIONS BASED ON ACID BASE
REACTIONS
-Finding End Point by Indicator
 TITRATIONS BASED ON ACID BASE
REACTIONS
-Finding End Point by Indicator
 TITRATIONS BASED ON ACID BASE
REACTIONS
-Finding End Point by Indicator

-For a polyprotic weak acid, always compare the pKa of the acid and the indicator to determine the relation in balanced
equation.
 TITRATIONS BASED ON ACID BASE
REACTIONS
Determining relation of unknown and given from law of conservation
involving titration of polyprotic weak acid.
1. A triprotic acid has a pKa values of 2.5, 6.9 and 10.4. What is its
relation with a certain base based on the law of conservation if the
indicator to be used is phenolphtahalein (pKa = 9.6)?
1 mole triprotic acid = 2 moles base since the pKa of phenolphthalein match that of the second pKa of the triprotic acid

2. A diprotic acid has a pKa value of 3.6 and 7.9. Determine its relation
based on the law of conservation if it will be titrate with a based and will
use methyl red indicator (pKa = 5.0).
1 mole diprotic acid = 1 mole base since the pKa of methyl red match that of the first pKa of the diprotic acid
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
1. A 50.00 mL sample of a citrus drink requires 17.62 mL of 0.04166 M NaOH to reach the
phenolphthalein end point. Express the sample’s acidity as grams of citric acid (a triprotic acid),
C6H8O7, per 100 mL. At. Wt: C = 12; H = 1; O = 16
I. Given: V sample = 50.00mL VNaOH = 17.62mL = 0.01762L MNaoH = 0.04166mole/L
MW C6H8O7 = (6)(12) + (8)(1) + (7)(16) = 72 + 8 + 112 = 192g/mole

II. Required: g citric acid / 100mL

III. Solution:

pKa Citric acid: pKa1 = 3.13 pKa2 = 4.76 pKa3 = 6.39 pKa php = 9.6
1 mole citric acid = 3 moles NaOH

Moles NaOH = M x V Moles NaOH = (0.04166mole/L)(0.01762L) = 0.000734mole = 7.34 x 𝟏𝟎−𝟒 mole

 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
1. A 50.00 mL sample of a citrus drink requires 17.62 mL of 0.04166 M NaOH to reach the
phenolphthalein end point. Express the sample’s acidity as grams of citric acid (a triprotic acid),
C6H8O7, per 100 mL.

Moles NaOH = 0.000734

1 mole C6H8O7 192 g

0.000734mole NaOH x ------------------------------- = 0.000245 mole C6H8O7 x ---------------- = 0.0470g / 50mL
3 moles NaOH mole
= 0.0940g / 100mL
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
2. Your company recently received a shipment of salicylic acid, C7H6O3, to be used in the production of
acetylsalicylic acid (aspirin). The shipment can be accepted only if the salicylic acid is more than 99% pure.
To evaluate the shipment’s purity, a 0.4208-g sample is dissolved in water and titrated to the
phenolphthalein end point, requiring 21.92 mL of 0.1354 M NaOH. Report the shipment’s purity as %w/w
C7H6O3. Salicylic acid is a diprotic weak acid with pKa values of 2.97 and 13.74.

I. Given: wt sample = 0.4208g VNaOH = 21.92mL = 0.02192L MNaoH = 0.1354mole/L

MW C7H6O3 = (7)(12) + (6)(1) + (3)(16) = 84 + 6 + 48 = 138g/mole

II. Required: %w/w C7H6O3

III. Solution:
wt
pKa C7H6O3 : pKa1 = 2.97 pKa2 = 13.74 pKa php = 9.6 %w/w = ---------------- x 100
Wt sample
1 mole C7H6O3 = 1 moles NaOH

Moles NaOH = M x V Moles NaOH = (0.1354mole/L)(0.02192L) = 0.0030mole

 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
2. Your company recently received a shipment of salicylic acid, C7H6O3, to be used in the production of
acetylsalicylic acid (aspirin). The shipment can be accepted only if the salicylic acid is more than 99% pure.
To evaluate the shipment’s purity, a 0.4208-g sample is dissolved in water and titrated to the
phenolphthalein end point, requiring 21.92 mL of 0.1354 M NaOH. Report the shipment’s purity as %w/w
C7H6O3. Salicylic acid is a diprotic weak acid with pKa values of 2.97 and 13.74.

Moles NaOH = 0.0030

1 mole C7H6O3 138 g

0.0030mole NaOH x ------------------------------- = 0.0030 mole C7H6O3 x ---------------- = 0.4140g
1 moles NaOH mole

0.4140g
%w/w = ---------------- x 100 = 98.38% Reject!
0.4208g
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
3. The purity of a pharmaceutical preparation of sulfanilamide, C6H4N2O2S, is determined
by oxidizing sulfur to SO2 and bubbling it through H2O2 to produce H2SO4. The acid is titrated
to the bromothymol blue end point with a standard solution of NaOH. Calculate the purity of the
preparation given that a 0.5136-g sample requires 48.13 mL of 0.1251 M NaOH.
I. Given: wt sample = 0.5136g VNaOH = 48.13mL = 0.04813L MNaoH = 0.1251mole/L
MW C6H4N2O2S = (6)(12) + (4)(1) + (2)(14) + 2(16) + (1)(32) = 72 + 4 + 28 + 32 + 32 = 168g/mole

II. Required: %w/w C6H4N2O2S

III. Solution:
wt
H2SO4 is a strong acid 1 mole H2SO4 = 1 mole S %w/w = ---------------- x 100
1 mole S = 1 mole C6H4N2O2S Wt sample
1 mole H2SO4 = 2 moles NaOH

Moles NaOH = M x V Moles NaOH = (0.1251mole/L)(0.04813L) = 0.0060mole

 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
3. The purity of a pharmaceutical preparation of sulfanilamide, C6H4N2O2S, is determined
by oxidizing sulfur to SO2 and bubbling it through H2O2 to produce H2SO4. The acid is titrated
to the bromothymol blue end point with a standard solution of NaOH. Calculate the purity of the
preparation given that a 0.5136-g sample requires 48.13 mL of 0.1251 M NaOH.
H2SO4 is a strong acid 1 mole H2SO4 = 1 mole S
1 mole H2SO4 = 2 moles NaOH 1 mole S = 1 mole C6H4N2O2S
Moles NaOH = 0.0060
1 mole H2SO4 1 mole S 1 mole C6H4N2O2S 168 g
0.0060mole NaOH x ------------------------------- x ------------------------------- x ------------------------------- x ----------------
2 moles NaOH 1 moles H2SO4 1 moles S mole

= 0.5040g 0.5040g
%w/w = ---------------- x 100 = 98.13%
0.5136g
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
4. The concentration of NO2 in air can be determined by passing the sample through a solution
of H2O2, which oxidizes NO2 to HNO3, and titrating the HNO3 with NaOH. What is the
concentration of NO2, in mg/L, if a 5.0 L sample of air requires 9.14 mL of 0.01012 M NaOH
to reach the methyl red end point
I. Given: vol sample = 5.0L VNaOH = 9.14mL = 0.00914L MNaoH = 0.01012mole/L
MW NO2 = (1)(14) + (2)(16) = 46g/mol

II. Required: mg/L NO2

III. Solution:
Wt in mg
HNO3 is a strong acid mg/L = ------------------------
Vol sample in L
1 mole HNO3 = 1 mole NaOH

1 mole HNO3 = 1 mole NO2 Moles NaOH = (0.01012mole/L)(0.00914L) = 0.0000925mole

 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
4. The concentration of NO2 in air can be determined by passing the sample through a solution
of H2O2, which oxidizes NO2 to HNO3, and titrating the HNO3 with NaOH. What is the
concentration of NO2, in mg/L, if a 5.0 L sample of air requires 9.14 mL of 0.01012 M NaOH
to reach the methyl red end point

1 mole HNO3 = 1 mole NaOH 1 mole HNO3 = 1 mole NO2

1 mole HNO3 1 mole NO2 46 g NO2

0.0000925mole NaOH x ------------------------------- x ------------------------------- x ---------------- = 0.004255g
1 moles NaOH 1 moles HNO3 mole
= 4.255mg

Wt in mg 4.255mg
mg/L = ------------------------ = ---------------- = 0.851mg/L
Vol sample in L 5.0L
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
5. 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 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 assuming that there are 6.38 grams of
protein for every gram of nitrogen in most dairy products.
I. Given: wt sample = 0.9814g VHCl = 50.00mL = 0.050 L M HCl = 0.1047mole/L
VNaOH = 22.84mL = 0.02284L MNaoH = 0.1183mole/L 1g N = 6.38g protein

II. Required: %w/w protein in cheese

III. Solution:
HCl is a strong acid wt
%w/w = ---------------- x 100
1 mole HCl = 1 mole NaOH Wt sample

1 mole HCl = 1 mole NH3 Total Moles HCl = mole main titration – mole from back titration
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
5. 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 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 assuming that there are 6.38 grams of
protein for every gram of nitrogen in most dairy products.
Main Titration Back Titration
Moles HCl = (0.1047mole/L)(0.05L) = 0.005235mole Moles NaOH = (0.1183mole/L)(0.02284L)
1 mole HCl
= 0.002702mole NaOH x -------------------------------
1 moles NaOH
= 0.002702mole HCl
Total Moles HCl = mole main titration – mole from back titration
= 0.005235mole – 0.002702mole = 0.002533mole HCl
TITRATIONS BASED ON ACID BASE
REACTIONS
= 0.002533mole HCl

1 mole NH3 1 mole N 14g N

0.002533mole HCl x ------------------------------- x ------------------------------- x ---------------- = 0.0355g N
1 mole HCl 1 mole NH3 mole

6.38g protein
= 0.0355g N x ------------------------------- = 0.2265g protein
1gN

wt 0.2265g
%w/w = ---------------- x 100 = ---------------- x 100 = 23.08%
Wt sample 0.9814g
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
6. Limestone consists mainly of CaCO3, with traces of iron oxides and other metal oxides. To
determine the purity of a limestone, a 0.5413-g sample is dissolved using 10.00 mL of 1.396 M
HCl. After heating to expel CO2, the excess HCl was titrated to the phenolphthalein end point,
requiring 39.96 mL of 0.1004 M NaOH. Report the sample’s purity as %w/w CaCO3. At. Wt.
Ca = 40; C = 12; O = 16
I. Given: wt sample = 0.5413g V HCl = 10.00mL = 0.01L M HCl = 1.396mole/L
VNaOH = 39.96mL = 0.03996L MNaoH = 0.1004mole/L MW CaCO3 = 100g/mole

II. Required: %w/w CaCO3

III. Solution: wt
%w/w = ---------------- x 100
HCl is a strong acid Wt sample
1 mole HCl = 1 mole NaOH
Total Moles HCl = mole main titration – mole from back titration
1 mole CaCO3 = 2 moles HCl
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
6. Limestone consists mainly of CaCO3, with traces of iron oxides and other metal oxides. To
determine the purity of a limestone, a 0.5413-g sample is dissolved using 10.00 mL of 1.396 M
HCl. After heating to expel CO2, the excess HCl was titrated to the phenolphthalein end point,
requiring 39.96 mL of 0.1004 M NaOH. Report the sample’s purity as %w/w CaCO3.

Main Titration Back Titration

Moles HCl = (1.396mole/L)(0.01L) = 0.01396mole Moles NaOH = (0.1004mole/L)(0.03996L)
1 mole HCl
= 0.004011mole NaOH x -------------------------------
1 moles NaOH
= 0.004011mole HCl
Total Moles HCl = mole main titration – mole from back titration
= 0.01396mole – 0.004011mole = 0.009949mole HCl
TITRATIONS BASED ON ACID BASE
REACTIONS
= 0.009949mole HCl

1 mole CaCO3 100g CaCO3

0.009949mole HCl x ------------------------------- x ---------------- = 0.4975g CaCO3
2 mole HCl mole

wt 0.4975g
%w/w = ---------------- x 100 = ---------------- x 100 = 91.91%
Wt sample 0.5413g
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
7. The alkalinity of natural waters is usually controlled
by OH–, HCO3–, and CO32–, which may be present
singularly or in combination. Titrating a 100.0-mL
sample to a pH of 8.3 requires 18.67 mL of a 0.02812
M HCl. A second 100.0-mL aliquot requires 48.12 mL of
the same titrant to reach a pH of 4.5. Identify the
sources of alkalinity and their concentrations in
milligrams per liter.
I. Given: VpH 8.3 = 18.67mL VpH 4.5 = 48.12mL

II. Required: Source of alkalinity

III. Solution: VpH 4.5 is more than twice the VpH 8.3
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
7. The alkalinity of natural waters is usually controlled by OH–, HCO3–, and CO32–, which may be
present singularly or in combination. Titrating a 100.0-mL sample to a pH of 8.3 requires 18.67 mL
of a 0.02812 M HCl. A second 100.0-mL aliquot requires 48.12 mL of the same titrant to reach a
pH of 4.5. Identify the sources of alkalinity and their concentrations in milligrams per liter.
I. Given: M HCl = 0.02812mole/L VpH 8.3 = 18.67mL (from CO3-2) VpH 4.5 = 48.12mL (from HCO3-1)
V sample = 100mL = 0.10L MW CO3-2 = (1)(12) + (3)(16) = 60g/mole
MW HCO3-1 = (1)(1) + (1)(12) +(3)(16) = 61g/mole
II. Required: mg/L of CO3-2 and HCO3-1
III. Solution:
HCl is a strong acid Wt in mg
mg/L = ------------------------
1 mole HCO3-1 = 1 mole HCl Vol sample in L
1 mole CO3-2 = 1 moles HCl
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
7. The alkalinity of natural waters is usually controlled by OH–, HCO3–, and CO32–, which may be
present singularly or in combination. Titrating a 100.0-mL sample to a pH of 8.3 requires 18.67 mL
of a 0.02812 M HCl. A second 100.0-mL aliquot requires 48.12 mL of the same titrant to reach a
pH of 4.5. Identify the sources of alkalinity and their concentrations in milligrams per liter.
1 mole CO3-2 = 1 moles HCl

Moles HCl = (0.02812mole/L)(0.01867L) = 0.000525mole

1 mole CO3-2 60g CO3-2

0.000525mole HCl x ------------------------------- x ---------------- = 0.0315g CO3-2 = 31.50mg CO3-2
1 mole HCl mole

Wt in mg 31.50mg
mg/L = ------------------------ = ---------------- = 315mg/L
Vol sample in L 0.1L
 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
7. The alkalinity of natural waters is usually controlled by OH–, HCO3–, and CO32–, which may be
present singularly or in combination. Titrating a 100.0-mL sample to a pH of 8.3 requires 18.67 mL
of a 0.02812 M HCl. A second 100.0-mL aliquot requires 48.12 mL of the same titrant to reach a
pH of 4.5. Identify the sources of alkalinity and their concentrations in milligrams per liter.
1 mole CO3-2 = 1 moles HCl
For the second aliquot: Total Volume = V from second aliquot – V consumed from the first aliquot
2 mole HCl 1L
-2
V HCl consumed from first aliquot = 0.000525mole CO3 x ------------------------------- x -------------------------------
1 mole CO3-2 0.02812 mole HCl

= 0.03733L = 37.33mL

Total Volume = 48.12mL – 37.33mL = 10.79mL

 TITRATIONS BASED ON ACID BASE
REACTIONS
Sample problems:
7. The alkalinity of natural waters is usually controlled by OH–, HCO3–, and CO32–, which may be
present singularly or in combination. Titrating a 100.0-mL sample to a pH of 8.3 requires 18.67 mL
of a 0.02812 M HCl. A second 100.0-mL aliquot requires 48.12 mL of the same titrant to reach a
pH of 4.5. Identify the sources of alkalinity and their concentrations in milligrams per liter.
1 mole HCO3-1 = 1 moles HCl

Moles HCl = (0.02812mole/L)(0.01079L) = 0.0003034mole

1 mole HCO3-2 61g HCO3-2

0.0003034mole HCl x ------------------------------- x ---------------- = 0.0185g HCO3-2 = 18.5mg HCO3-2
1 mole HCl mole

Wt in mg 18.5mg
mg/L = ------------------------ = ---------------- = 185mg/L
Vol sample in L 0.1L