ANALYTICAL CHEMISTRY NOTES II

Quantitative Methods of Analysis

Quantitative methods of analysis indicates the amount of each substance in a sample.
They are traditionally classified as gravimetric, volumetric, and instrumental.
Gravimetric analysis is one of the most accurate and precise methods of
macroquantitative analysis. The analyte is selectively converted to an insoluble form.
The separated precipitate is dried or ignited, possibly to another form, and is accurately
weighed. From the weight of the precipitate, and a knowledge of its chemical
composition, the weight of the analyte in the desired form is calculated.
Volumetric or titrimetric methods include a group of analytical methods that are
based on determining the quantity of the reagent of known concentration that is required
to react completely with the analyte. There are several types of titrimetric methods:
volumetric titrimetry which involves measuring the volume of a solution of known
concentration that is needed to react essentially completely with the analyte; gravimetric
titrimetry, which differs from volumetric only in that the mass of the reagent is measured
instead of its volume. The third type is coulometric titrimetry, a type of titrimetry in
which the quantity of charge in Coulombs required to complete a reaction with the
analyte is the measured quantity.
Titirimetric methods have the advantage over gravimetric methods because of
superior speed and convenience without sacrificing the accuracy and precision of the
process. The methods can be applied to
1. Acid-base (acidimetry-alkalimetry)
2. Complexation (complexometric)
3. Redox
4. Precipitation

Terminology used in Volumetric titrimetry

1. Analyte is the substance sought for or the test substance
2. Standard solution (or a standard titrant) is a solution of known concentration that is
used to carry out titrimetric analysis, or it is the substance reacting with the analye.
3. Titration is a process by which the quantity of analyte in a solution is determiend
from the amount of standard reagent it consumes. It is performed by slowly adding a
standard solution from a buret or other liquid-dispensing device to a solution of the
analyte until the reaction between the two is judged complete. The volume or mass
of reagent needed to complete the titration is determined from the difference
between the initial and final readings. Titration is widely used in analytical
chemistry to determine acids, bases, oxidants, reductants, metal ions, protein, and
many other species.
4. Standardization is the process of ascertaining the accurate concentrations of the titrant
by reacting with a primary standard.
5. Primary standard is a reagent of highest purity used to standardize a standard solution.
6. Equivalence point refers to that point in a titration in which an equivalence or
stoichiometric amount of titrant is added to the analyte.
7. End point is the point at which the reaction is observed to be complete through
changes in some properties of the solution.
8. Back-titration is a process in which an excess of a standard solution used to consume
an analyte is determined by titration with a second standard solution.
9. Indicators are substances that are often added to the analyte to produce an observable
physical change (end point) at or near the equivalence point.
10. Stoichiometirc reaction is one in which a definite, reproducible relationship exist
between the reacting substances.
11. Titration error is the difference in volume or mass between the equivalence point and
the end point in a volumetric method.
Et = Vep - Veq Where:
Vep = the actual volume of the reagent or
volume at the end point
Veq = the theoretical value to reach the
equivalence point.

Requirements of a Titration
All successful titration are based on reactions that are stoichiometric, fast, and for
which there is a suitable means of estimating the equivalence point. The following are
the requirements of titration:
1. The reaction should be stoichiometric; there should be a well-defined and known
reaction between the analyte and the titrant.
2. The reaction should be rapid.
3. There should be no side reactions and the reaction should be specific.
4. There should be a marked change in some property of the solution when the reaction
is complete.
5. The end point should coincide with the equivalence point.
6. The reaction should be quantitative.

A primary standard is a highly purified compound that serves as a reference material

in volumetric methods. The accuracy of a method is critically dependent on the
properties of this compound.

Requirements of a Primary Standard

1. The standard must be of very high purity, preferably 99.9% with about 0.01-0.2%
impurity
2. It should be stable in solid form and stale to dying temperature.
3. It should have high molar mass to minimize error in weighing.
4. It should have high solubility in the titration medium.

Standard solutions play a central role in all titrimetric methods of analysis. The
following are the requirements of an ideal standard solution.
1. It should be sufficiently stable so that it is necessary to determine it concentration
only once.
2. It should react rapidly and completely with its analyte so that satisfactory end points
are realized.
3. It should undergo a selective reaction with the analyte that can be described by a
balanced equation.

Solution Preparation (A Review)

Example:
1. A standard 0.0100M Na+ is required in the analysis. Describe how 500mL of this
solution is prepared from primary standard Na2CO3.
Given:
Conc. Of std. solution = 0.10M Na+
V of std. solution = 500mL
Required:
Wt. Of Na2CO3
Solution:
MW of Na2CO3 = 106 g/mole

Wt. of Na2CO3 needed =

= 0.265g
Solution preparation:
Dissolve 0.265g Na2CO3 in water and diluting to 500mL.
2. How would you prepare 50mL portions of standard solution that are 0.005M and
0.002M in Na+ from a standard solution that is 0.01M Na+?
Given:
Conc. Of std. solution = 0.10M Na+
Required:
Volumes of 0.01M std. solution needed to prepare 50ml of 0.005M and 0.002M
Na+
Solution:
Dilution formula: Cd x Vd = Cs x Vs
a) For 0.005M Na+ solution:

b) For 0.002M solution:

Solution preparation:
a) Measure 25mL of 0.01M Na+ solution and dilute it with H 2o to exactly
50mL.
b) Measure 10mL of 0.01M Na+ solution & dilute it to exactly 50mL.

Titration Curve for Acid-Base Titration

The construction of a titration curve for acid-base titration helps us to monitor the
changes in pH during the reaction of titrant, analyte, and indicator. We can also
determine the equivalence point as well as the end point of the titration process. Titration
curve is made by plotting the value of the titrant added versus the pH. The pH can be
measured experimentally with a pH meter or it can be calculated using equations derived
from neutralization and chemical equilibrium.

A. Titration curve for strong acid titrated with strong base

There are 3 distinct regions of the curve which corresponds to 3 major changes
in slope.
1. The pH starts low, reflecting high [H +] of the strong acid, and increases
gradually as the acid is neutralized by the added base.
2. Suddenly the pH rises steeply. This rise begins when the moles of OH- that
have been added nearly equal the moles of H+ originally present in the acid.
3. Beyond this steep portion, the pH increases slowly again as more base is
added.
Below is a typical titration curve for strong acid-strong base titration:

In summary:
Region Major Constituent Comment
1. Before the equivalence point HCl + NaCl Treat as strong acid
2. At the equivalence point NaCl Treat as pure solvent
3. After the equivalence point NaCl + NaOH Treat as strong base

Example-1. Calculate the pH of the solution when 50mL of 0.1M HCl has been
titrated with 0, 5, 30, 50, and 60mL of 0.1M NaOH
Solution:
at 0mL; before the addition of any titrant, HCl is the only component of the
solution; [H+]=0.1 and pH=-log 0.1=1.0
at 5.0 mL, 0.1M NaOH added; the constituent of the solution is HCl + NaCl,
Since: HCl + NaOH → NaCl + H2O
Comparing the no. of mmoles of each components;

No. of mmoles HCl =

= 5.0 mmoles
 No. of mmoles NaOH added =
= 0.5 mmoles
Solving for no. of mmoles HCl unneutralized;
No. Of mmoled HCl unneutralized = 5.0 mmole-0.5 mmole
= 4.5 mmoles
In 55mL solution:

⁖ [H+] = 0.0818; pH = -log 0.0818

= 1.087
at 30mL NaOH added: VT = 50+30 = 80mL

No. of mmoles NaOH added =

= 3.0 mmoles
No. Of mmoles HCl unneutralized = 5.0mmols-3.0mmols
= 2.0mmoles
Solving for concentration of HCl in solution;

[H+] = 0.025; pH = -log 0.025 = 1.6

at 50mL NaOH added: VT= 50 + 50 = 100mL

No. of mmoles NaOH added =

= 5.0 mmoles
At this point, the acid is completely neutralized by the NaOH, we have an
equal number of H+ and OH-: pH = 7
at 60mL NaOH added: VT=50+60 = 110mL

No. Of mmoles NaOH added =

= 6.0 mmoles
At this point, NaOH is in excess oveer that of HCl.
No. of moles in excess = 6.0-5.0
= 1.0 mmol
Solving for the conc. of NaOH in solution;

[NaOH] =
= 0.0091
[OH ] = 0.0091; pOH = -log 0.091
-

= 2.04
⁖ pH = 11.96 beyond the equvalence point

B. Titration curve for weak acid titrated with strong base

 A weak acid-strong base titration can be divided into four regions, each
corresponding to a different solution composition.
Region Major Constituent Comment
1. Before the addition of titrant CH3COOH Treat as weak acid
2. Before the equivalence point CH3COOH + CH3COONa Treat as buffer
3. At the equivalence point CH3COONa Treat as weak base
4. After the equivalence point CH3COONa + NaOH Treat as strong base

Example-2. Calculate the pH of the solution resulting when 20mL of 0.10M

CH3COOH has been titrated with 0, 10, 20, and 30mL of 0.10M NaOH.
Ka=1.76x10-5
Solution:
at 0mL: 0.1m CH3COOH; CH3COOH ↔ CH3COO- + H+

Ka =

Ka =

[H+]=
= 1.326 x 10-3
pH = -log 1.326 x 10-3 = 2.88
at 10mL, 0.1M NaOH: VT = 20+10 = 30mL , Eqn: CH3COOH + NaOH = CH3COONa + H2O
No. of mmoles CH3COOH = 20mL x 0.10 mm/mL
= 2.0 mmoles
No. of mmoles NaOH added = 10mL x 0.10 mm/mL
= 1.0 mmole
No. of mmoles CH3COOH unneutralized = 2.0 - 1.0
 = 1.0 mmole
Solving for concentration of CH3COOH and CH3COONa in 30mL solution;

[CH3COONa] = = 0.0333

[CH3COOH] = = 0.0333
Using the Henderson-Hasselbach equation;

pH = pka + log

pH = 4.75 + log
pH = 4.75
at 20mL NaOH added: VT= 20+20 = 40mL
No. of mmoles NaOH added = 30mL x 0.1 mmol/mL
= 2.0 mmols
At this point of titration, there is equal no. of mmoles of acid and base,
complete neutralization of CH3COOH occurs.

Solving for conc. of CH3COONa; CH3COONa = = 0.05

The resulting salt will undergo hydrolysis:
CH3COONa + HOH → CH3COOH + NaOH or
CH3COO- + HOH → CH3COOH + OH-

Solving for [OH-]; OH- = where:

Kw = ion-product of H2O
Ka = ionization product of the
weak acid
CA = concentration of salt
Substituting values:

[OH-] =
= 5.33 x 10-6
pOH = -log 5.33 x 10-6
= 5.27
pH = 8.727
At 30mL NaOH added: VT = 20 + 30 = 50mL
No. of mmoles NaOH added = 30mL x 0.1 mmol/mL
= 3.0 mmoles
At this point, NaOH is in excess;
No. of mmoles excess NaOH = 3-2
= 1.0 mmole
Solving for the concentration of excess NaOH;
 [NaOH] = = 0.02
[OH-] = 0.02
pOH = -log 0.02
= 1.699
⁖ pH = 12.3

Formulas for salts undergoing hydrolysis:

a. Salts of weak acid & strong base: [OH-] =

b. Salts of weak base & strong acid:

[H+]= where:
Kw = ion-product of H2O
Kb = ionization constant of base
CB = concentration of salt
Assignment:
I. What are the common acid-base indicators for acidimetry-alkalimetry? Indicate the
pH range and color change for each indicator.
II. A. Give at least 3 primary standards for standardization of (a) HCl, H2SO4, (b)
NaOH, KOH, Ba(OH)2
B. State the properties of each primary standards and the limitations as to its
application.
III. Solution Preparation (A Review) [Show your solutions.]
Describe the preparation of
a. 750mL of a solution that is 0.09M in K+, from solid K4Fe(Cn)6.
b. 500mL of 2% (W/V) aqueous BaCl2 from a 0.500M BaCl2 solution.
IV. Titration Curves. Solve the ff. Problems
1. A 25mL aliquot of 0.1M NaOH is titrated with 0.10M HCl. Calculate the pH of
the solution after the addition of 0, 5, 10, 25, 30, 35, and 40mL of acid and
prepare a titration curve from the data by plotting the pH versus the volume of
the titrant.
2. Calculate the pH at 0, 10, 25, 50, and 60mL of titrant in the titration of 50ml,
0.1M HCOOH with 0.1M NaOH. ka= 1.80x10-4