INTRODUCTORY ANALYTICAL CHEMISTRY 1 - Final

MUNI UNIVERSITY
CHEMISTRY DEPARTMENT.
CHM 2201: INTRODUCTORY ANALYTICAL CHEMISTRY (3 CU)

COURSE FACILITATOR: Godfrey Muhwezi.
Course Outline
WEEK CONTENT MODE OF DELIVERY
1 Introductory Lecture- Discussion, Lectures
Definition, application of Analytical Chemistry and the

Analytical Process and applications
Methods of representing concentrations.
Methods of sampling.
 Accuracy,
 precision, causes and estimation of errors
2 Titrimetric. Practicals, Discussions and
Lectures
 Titrimetric method, acid-base,
 Redox, Complexometric,
 Precipitation
3 Non-aqueous vis-à-vis aqueous titrations Discussion and Practicals.
4 Gravimetry – factors affecting solubility of precipitate: Discussion, Lectures,

excess reagent, Practicals
 Ionic strength, pH and solvent

5 Spectroscopic methods: Practicals.
 UV-visible and IR spectrometry; principles and

instrumentation.
 Separation techniques. Gas chromatography
principles, instrumentation and applications
Muhwezi Godfrey,Chem Department pg. 1

6 Electrophoresis: Lectures and Discussions
 Apparatus and applications.

 Ion exchange: synthetic ion-exchange materials;
mechanism of ion-exchange, selectivity, various
applications.
 Solvent extraction, fundamental principles,
practical considerations and applications
Practicals
7 Acid-base Titration Practicals.
Standardisation of hydrochloric acid, sodium hydroxide

with sodium carbonate and sulphuric acid respectively
8  Determination of sodium carbonate in an impure Practicals
salt.
 Determination of sodium carbonate and sodium
bicarbonate in a mixture
9  Determination of carbonate and hydroxide in Practical guided sessions.
solution.
 Analysis of sodium carbonate and bicarbonate in
rock salt.
 Analysis of various types of cement, Hima,
Bambuli, Tanga and Tororo Cement.
 Determination of ammonia in an ammonium salt.
 Determination of Boric acid.
 Analysis of pharmaceutical preparations.
10 Oxidation – Reduction Titrations Practicals (Laboratory
work)
 Standardization of KMNO4 against Arsenic (III)
oxide.
 Determination of iron (II) and Iron (III) in solution.
 Determination of total iron in environmental
samples.
11 Argentometric titrations: Discussions, Practicals
(student aided)
 Standardization of silver nitrate solution.
 Determination of chloride by the Volhard method.
 Determination of chloride by Fajans method.
Analysis of Katwe, Magadi and rock salts
12 Iodometric titrations Discussion, Practical
 Standardization of thiosulphate solution.

 Analysis of copper in an ore from Kilembe.
 Determination of formaldehyde.
 Determination of ammonia in ammonium salt.
 Determination of ammonia in urea –fertilizers.

Laboratory sessions.
13 Complexometric titrations Discussions, Practicals.
 Preliminary observation in complex formation

 Standardization of EDTA.
 Determination of total hardness in tap water.
 Determination of calcium and magnesium in the
mixture.
Determination of Ca and Mg in limestone from W. Uganda
14 Field visit (trip) to a cement Factory and a Pharmaceutical Practicals, guided study
company. trip/ tour
15  Indirect determination of sulphate. Practical

 Direct determination of lead.
Analysis of Bi-Pb, Cd-Sn in alloys
Suggested Reading List
1. Skoog, West, Holler and Crouch (2004). Fundamentals of Analytical Chemistry . 8th edition,
Thomson, London.
2. Gary D. Christian (1994). Analytical Chemistry. John Wiley and Sons Inc., New York
3. Jeffery G.H., Bassett J., Denney R.C, and Mendham J (1989). Vogel’s Textbook of quantitative
chemical analysis. 5th Edition. Longman, London Belcher & Nutten (1970). Quantitative Inorganic
Analysis 3rd Edition. Butter Worths, London
4. Skoog and West, 1963. Fundamental of Analytical chemistry (2 nd ed). Holt Rinehart and
Winston, Inc: London

Introduction
This lecture introduces you to one of the most important areas of chemistry. Analytical chemistry
is a branch of chemistry that that deals with separating, identifying and quantifying the relative
amounts of the components of the sample that are to be determined (analyte). A complete
chemical description of a sample of matter requires establishment not only of the types of species
present but also of their amounts. These are the question to which analytical Chemistry is
directed.
Objectives
By the end of this lecture, you should be able to; -
 Define analytical chemistry

 Site several areas of analytical chemistry and give relevant examples
 Differentiate between qualitative and quantitative analysis
 Suggest different uses of analytical chemistry
The scope/application of analytical chemistry
Analytical chemistry cuts across almost all fields of the subject. There are several different areas
of analytical chemistry.
1- Clinical analysis – requires collection of blood urine, feaces, cellular fluids etc. for use in
diagnosis
2- Pharmaceutical analysis – this establishes the physical properties, toxicity, metabolites,
quality control etc.
3- Environmental analysis- this include pollutants, soil and water analysis pesticides
4- Forensic analysis- analysis related to criminology; DNA figure printing, finger print
detection, blood analysis.
5- Industrial quality control- analysis required by most companies to control product quality.

6- Bio- analytical chemistry and analysis- involves detection and/or analysis of biological
components (i.e. proteins, DNA, RNA, carbohydrates, metabolites etc.). This often overlaps
many areas.
The focus of the course is an introduction experience in the qualitative and quantitative analysis
with some methods of analysis separation.
Qualitative analysis comprises the tests that enable the chemist to determine what species are
present and perhaps their state of combination as well.
Quantitative analysis on the other hand, provides the means for determining how much of some
components is present in a unit quantity of sample.
Similarities between qualitative and quantitative analysis
 Both require the measurement of some chemical or physical property of the systems,
which in turn can be related to the information desired.
 Both require preliminary treatment to ensure that the analytical observation when it is
made, measure only the component of interest.
Differences between qualitative and quantitative analysis
 In contrast to the similarities above, many problems confronting the analysts are unique
only to quantitative measurement. Here, for example, he must work with the aim of
keeping losses of the components he seeks, to a tolerable minimum during the
preliminary phases of the analysis. It is ordinarily a requirement that the reaction on
which he bases his analysis will proceed to essential completion relationship between in
a single product. Finally, there must be some reproducible relationship between the
property or quantity he measures and the amount of the species he is determining. These
added conditions limit the reactions that are suitable for quantitative work.
 Quantitative information is not a prerequisite for a successful qualitative analysis on the
other hand, a qualitative description of the sample is ordinary essential to selection of a
suitable quantitative methods.

Importance of analytical chemistry in the field of science
Historically analytical chemistry has always occupied a vital position in the development of the
field. Early chemistry was principally analytical in nature. Only as the body of experimental fact
increased did it become possible for the chemist to specialize according to his interests- in other
field. Irrespective of choice, however, he continued to rely heavily upon analytical methods and
techniques to provide him with experimental information. Analytical chemistry thus, assumed
the supporting role of an indispensable tool in advancing the state of knowledge in the fields of
inorganic, organic and physical chemistry.
The situation is as applicable to the chemistry of today as to that of the past.
 Every experimental investigation relies, to an extent, upon the results of analytical

measurement. A thorough background in analytical chemistry is therefore a vital
necessity for all who aspire to be chemists, regardless of their field of specialization.
 Investigators in virtually all physical and biological sciences are obliged to make use of
analytical data in the course of their work.
 The physician relies heavily upon the results of the analysis of body fluids in making his
diagnoses.
 Analytical techniques are indispensable in the biochemist’s study of living matter and
metabolic processes.
 The classification of a mineral is incomplete without knowledge of its chemical
composition. Analytical methods are therefore useful in geology.
 Analytical techniques are employed by the physicists in identifying the products of high-
energy bombardments.
The role of analytical chemistry in modern industry is difficult to overestimate. Virtually every
item of commerce has been subjected to analytical testing at one or more stages in its
manufacture. The clothes we wear, the food we eat, the drugs we require, and the automobiles
we drive – all these and more require that aid of analytical chemistry to assure the production of
goods having uniform quality and characteristics.

Finally, above and beyond these practical considerations the study of quantitative analysis
requires development of systematic and orderly work habits as well as intellectually honest
observations. These traits are worthy of cultivation regardless of one’s ultimate field of
endeavor.
Classification of methods of quantitative analysis
Ultimately in every quantitative analysis, there is a final measurement whose magnitude can be
related to the amount of the species being determined. It is convenient to classify the methods of
quantitative analysis according to the nature of this final measurement. Thus, the methods of
quantitative analysis can be classified according to the nature of this final measurement. Thus,
the methods can be classified as follows;
Gravimetric analysis; here the final measurement involves the determination of a weight.
Volumetric analysis. This involves the measurement of a volume
Colorimetric analysis: This consists of establishing indirectly the amount of radiant energy that
has been absorbed by the sample.
Electro analytical methods. These are based upon the determination of some electrical property
as the final step. A classification of common quantitative techniques on this basis is shown in the
following table; -
General classification Sub-classification Quantity measured

Gravimetric Direct method Weight of compound
indirect method species ,loss of weight due
to volatilization of species.
Volumetric Titration methods Volume of solution that is
chemically equivalent to the
species sought
Gas analyses Volume of a gaseous
species produced or

Emission spectroscopy consumed.
Radiation emitted by species
Absorption spectroscopy
including colorimetry Radiation absorbed by
Polarimetry species.
Rotation of polarized light
Turbidimetry by species
Scattering of radiation by
Nephlometry species in suspension.
Potentiometry Potential of an electrode in

equilibrium with the species
Electro- analytical Conductimetry Conductance of a solution of

the species
Coulometry Quantity of electricity

equivalent to the species
Polarography Current associated with

reaction at a polarizable
electrode.
Miscellaneous High- frequency methods Capacitance of solution of
species.
Mass spectroscopy Mass- to –charge ratio of
decomposition products of
species
Radiochemical methods Radioactive decay of species
Thermal- conductivity Thermal conductance of
methods species
Enthalpy titrations Heat of reaction of species.

From a historical standpoint, the majority of early analytical methods were either gravimetric
or volumetric procedures; for this reason, these are sometims known as classical methods of
analysis. Procedures based on the measurement of optical, electrical, thermal and other
properties were developed later and as a group are sometimes termed instrumental methods.
In many respects this two- way classification is unfortunate and could be misleading, for it
implies that classical and instrumental methods are basically different. In reality,
fundamental differences between the two categories do not exist.
 Both are based upon the correlation of a physical measurement with concentration
 Both employ an instrument for this measurement; to the extent that neither is
specific. Preliminary separation steps are needed for both types of analyses.
The classification of methods as classical or instrumental is thus founded largely on

chronological development and should not confuse the learner.
The Analytical process
Introduction
It is important to recognize that the final measurement is but one step in a sequence of operation
that leads to the knowledge of the concentration of a component in a sample of matter. Below are
the steps that make-up the analytical process.
Objectives
By the end of the lecture, you should be able to;
 State and explain the different steps taken when analyzing any given environmental
sample.
1- Defining the problem and choosing the method to use
Before the analyst can design an analysis procedure, he or she must know what information is
needed and what type of sample is to be analyzed. This will dictate how the sample will be
obtained, how much is needed, how sensitive the method must be, how accurate and precise it

must be and what separations may be required to eliminate interferences. Once the required
measurement is known, then the analytical method to be used will depend on a number of factors
which include the following;
 Analyst’s skills and training in different techniques and instruments

 The facilities
 Equipment and instrument available
 The sensitivity and precision required and accuracy
 The cost and budget available and how soon the results are needed.
The selection of method is vital step in the resolution of an analytical problem. The choice is
frequently difficult, requiring experience as well as intuition on the part of the chemist.
An important consideration in selection is the accuracy required. Unfortunately, high reliability

nearly always requires a large expenditure of time; the method chosen may thus, of necessity,
represent a compromise between assurance and economics.
A second consideration also related to economic factors, is the number of samples to be

analysed. If there are many, the chemist can afford to use a method that requires such
preliminary operations as the assembling and calibrating of instrumental equipment and the
preparing of standards solutions. On the other hand, with only a single sample or a few samples,
he may find it more convenient to select a procedure that avoid such preliminary steps.
Finally, the method chosen will always be governed by the complexity of the sample being
analysed and the number of components in the sample for which quantitative information is
needed.
2. Obtaining a representative sample
A chemical analysis is usually performed on only a small portion of the material to be

characterized. To produce meaningful results, an analysis must be performed on a sample whose
composition faithfully reflects that of the bulk of material from which it was taken. Where the
bulk is large and inhomogeneous, great effort is required to produce a representative sample. The
chemist cannot afford to proceed with an analysis until he has convinced himself that the fraction

of the material with which he plans to work is truly representative of the material from which the
sample is taken.
3. Preparation of the laboratory sample for analysis
Often, solid material must be ground to reduce particle size and then be thoroughly mixed to
ensure homogeneity. The former operation is particularly important with difficult soluble
substance since the rate of solubility increases greatly by reduction in particle size. The removal
of absorbed moisture is another preparatory operation of importance with most solid samples.
Any tendency toward absorption or desorption of water will cause the percentage composition of
a substance to depend upon the humidity of its surrounding at the time of the analysis. In order to
avoid the problems arising from such variations, it is common practice to base the analysis on a
dry sample. Frequently, heating of the material to about 100 0C or exposing it to a dry
atmosphere for suitable periods of time is sufficient to remove moisture;
4- Obtaining a measured quantity of the sample
Quantitative analytical results are usually reported in relative terms, that is, in some way which
expresses the quantity of the desired component present per unit weight or volume of sample. In
order to express the results in a meaningful manner, it is therefore, necessary to know the weight
or volume of the sample upon which the analysis is performed. The purpose of all subsequent
steps is the determination of the weight of the desired species present in this quantity of sample.
5- Solution of the sample
If, as is frequently the case, it is necessary to bring the sample into solution, the choice of solvent
and the selection of optimum conditions for its use become important preliminary steps to the
analysis. Ideally, the solvent chosen for an analysis should be effective in dissolving the entire
sample in a reasonable period of time. In addition, the chemical compositions of the solvent
should not interfere with subsequent steps in the analysis or should be easily removable if they
do.
In general, it is advisable to employ the mildest solvent and the lowest temperature that will put
the sample into solution within a reasonable time. Concentrated reagents may produce reactions
that are violent enough to cause physical loss of solid sample and these are to be avoided

whenever possible. Elevated temperatures should also be avoided in order to reduce the danger
of losing components of interest by volatilization.
6. Separation of interfering substances
Interferences are substance that prevent direct measurement of the analyte (the thing to be
analysed) and must be removed. Few, if any, chemical or physical properties of importance in
analysis are unique to a single chemical species, instead, the reactions used and the properties
measured are characteristic of a number of elements or compounds. This lack of truly specific
reaction and properties adds greatly to the difficulties faced by the chemists when undertaking an
analysis. It means that a scheme must be devised for isolating the species of interest from all
others present in the original materials that produce an effect upon final measurement.
Compounds or elements that prevent the direct measurement of the species being determined are
called interferences and their separation prior to the final measurement constitutes an important
step in most analyses. No hard and fast rule can be given for the elimination of interferences;
this problem is often the most demanding aspect of the analysis.
7. The completion of the analysis
The physical or chemical property proportional to the analyte concentration is measured. All
preliminary steps in an analysis are undertaken in order to make the final measurement a true
gauge of the quantity of the species being determined.
8. Calculation and interpretation of results
The conversation of the experimental data from an analysis to a concentration is ordinarily

straight forward. The analytical result is incomplete, however, without some indication of its
reliability and the estimation of probable accuracy is an important part of the analytical
processes. Such an evaluation is usually based on previous experience with the method and
consideration of the reproducibility of the data.
While the steps listed above are common to all quantitative methods, it must be recognized that
their relative importance in a particular analysis may vary widely, that which represent the most
formidable aspect of one determination may actually be of negligible importance in another.

It should be further pointed out that the mechanical skills necessary to the completion of a
successful analysis can be readily taught to persons having little or no scientific background.
Indeed, a routine analysis may be performed better by the technician than by his more highly
trained supervisor. However, an intelligent appraisal of the factors of importance in the several
steps comprising a quantitative analysis requires more chemical knowledge than that possessed
by the technician. It is this added knowledge that the learners should strive to achieve.
The Language of Analytical Chemists.
Qualitative analysis: An analysis in which we determine the identity of the constituent

species in a sample.
Quantitative analysis: An analysis in which we determine how much of a constituent
species is present in a sample.
Analytes: The constituents of interest in a sample.
Matrix: All other constituents in a sample except for the analytes.
A selective reaction or test is one that can occur with other substances but exhibits a
degree of preference for the substance of interest.
A specific reaction or test is one that occurs only with the substance of interest.
Note: few reactions are specific but many exhibit selectivity.
Detection limit: A statistical statement about the smallest amount of analyte that can be
determined with confidence.
Precision and Accuracy
Precision describes the reproducibility of a result. If you measure a quantity several
times and the values agree closely with one another, your measurement is precise. If the
values vary widely, your measurement is not very precise.
Accuracy describes how close a measured value is to the “true” value. If a known
standard is available, accuracy is how close your value is to the known value.
Important chemical concepts
Introduction

This part reviews basic principles and units of measurement (hopefully learned in previous work)
Objectives
By the end of this lecture, you should be able to; -
 Define concentration in terms of all the common units

 Use specific gravity to determine the concentration of liquids
Units of concentration
Concentration is expressed in a variety of ways. The most general definition. Concentration =

amount of solute in a given amount of solution. Common units used by chemists include; -
1- Molarity (M) = number of moles solute per liter of solution

2- Formality (F) = number of moles solute per liter of solution
3- Normality (N) = number of equivalents of solute per liter of solution
Activity
Read about equivalent weights
(a) For acid –base reactions, I equivalent = 1 mole of hydrogen ions (or 1 mole of hydroxide
ion) donated.
(b) For oxidation – reduction reactions, 1 equivalent = 1 mole of charge
(c) Normality must be specified with respect to a definite reaction
(d) Normality = (formality) (number of electrons transferred) or
= (formality) `number of hydrogen ions neutralized)
= (formality) (number of hydroxide ions neutralized)
For example: 1.00N Na2 CO3
In the reaction, CO3 2- + H+ H2O + CO2
1 liter of 0.100N Na2 CO3 contains by definition, 0.100eqvilent of Na2CO3

0.100eq Na2 CO3 (1mol/2eq Na2CO3) = 0.0500molNa2CO3
In simple terms, 0.1NNa2CO3 = 0.005M Na2CO3
f. The equivalents = weight/equivalent weight. The equivalent weight equals the formula weight
divided by the number of electrons transferred or the number of hydrogen ions (Hydroxide ions)
neutralized (i.e. it is the weight that corresponds to one equivalent).
4. Molality (M) = number of moles of solute/number of kilograms of solvent
5. Osmolarity (O or OSM) = number of total moles of particles/number of liters of solution
6. Parts per thousand (ppt)
Cppt = (Weight of substance /weight of solution) x 10-3 ppt
7. parts per million (ppm)
Cppm= (Weight of substance /weight of solution) x 10-6 ppm
Note that for dilute, aqueous solutions, 1ppm = 1mg/l = 1:ml -1 because 1 L approximately
equals 1 kilogram of solution.
8. Percent concentration (or part per hundred) can be expressed several ways; -
a. Weight percent (w/w)
Cww = (weight solute/weight solution] x 100%
B. Volume percent (v/v)
Cww = (volume solute/volume solution) x 100%
c. Weight / Volume percent (w/v)
Cww= (weight solute (g)/volume solution (ML) x 100%
d. Usage of percent concentration varies. For example, commercial aqueous reagents are usually
sold in a weight % (w/w).

1. 37% w/w HCl means 37gHCI/100g solution
2. To calculate the morality of the HCI requires knowledge of the solution
Density and specific gravity
Density = mass volume
1- The units are usually grams/ml.

2- Be careful about other units
Specific gravity = (mass of substance)/ mass of equal volume water)
= (density of substance) density of water
1. Note that the temperature must be specified for specific gravity

2. Specific gravity is a unit less ratio (i.e. it does not matter what the units are so long the
same units are used for the substance and water.
3. Specific gravity is more often used in commerce and commercial reagent labeling than
density
Activity
Calculate the molarity of a 69% solution of nitric acid with a specific gravity of 1.4.2

Errors in chemical analysis
Introduction
It is impossible to perform a chemical analysis that is error free. Each of the measurements in an
analysis is subject to uncertainty. For the present,we need only to recognize that these
uncertainties are responsible for the variation observed among measurement of the same
quantity. In practice, the chemist generally makes replicate measurement, his reasoning being
that the confidence in which his results can be held is increased by demonstration of their
reproducibility. Having obtained several values for same quantity, he is then confronted with the
problem of defining the best value for the measurement.
Objectives
By the end of this lecture, you should be able to;
 Identify the different errors that an analytical chemist face

 Solve all the simple problems related to error
Our goals are to minimize errors and to calculate the size of the error. Examples of errors in
chemical analysis include;
1- Accuracy without precision

2- Precision without accuracy
One must establish the reliability of the data (i.e. establish limits within which the true value lies
with a known probability).
The limits and reliability must be determined by statistically valid methods
We will concern ourselves with; -
1- Types of errors
2- Methods of recognizing errors
3- Techniques for estimating and reporting of errors

Significant figures
We must review significant figures before considering errors and error analysis. Significant
figures in a measurement include all certain digits plus the first uncertain digit.
1- For lined, scales, estimate one digit smaller than the smallest division on the scale. For
example
a. Graduated cylinders
b. Meter sticks
c. Mohr pipettes
2. For electronic/digital all displayed digits are assumed significant and the last digit is
assumed to be only uncertain digit.
Significant figure “rules” for reporting data
1- All nonzero digits are significant

2- Zero used to locate a decimal point are never significant (i.e. zero to the left of a nonzero
digit).
3- Zeros used to indicate the accuracy of the measurement are significant (i.e. zeros to the right
of a nonzero digit in the presence of a decimal point)
4- Trailing zeros (not indicating accuracy) may or may not be significant
a. If a decimal is present, they are significant
b. If a decimal is not present, they are not significant
c. It is always best to use scientific notation
Absolute and relative uncertainty
Absolute uncurtaining is an expression of the uncertainty of a measurement. Usually, it is plus-

minus the last digit = absolute uncertainty. For example.
10.20g = implies that the measurement is +/- 0.01g
Absolute uncertainty = (absolute uncertainty)/ measurement. For example
10.20g = absolute uncertainty = +/-0.01g

Relative uncertainty = (0.01g)/10.20)
= 0.0009803
= 0.001
1. Relative uncertainty can be expressed as in a variety of methods

a. A. % (or pp.) = (absolute uncertainty/measurement] x 100%
b. Ppt = (absolute uncertainty)/measurement] x 100ppt
c. Ppm= [ absolute uncertainty)/measurement] x 10+6 ppm
In the example above,
10.20+/- 0.01 = relative uncertainty in ppt is
Ppt = [(absolute uncertainty)/measurement) x 1000ppt
= [0.01/10.20] x 1000ppt
= 1ppt
d. Sample problem: A burette is used to measure 5.00ml

5.00+/- 0.01ml =
Absolute uncertainty = 0.01
Relative uncertainty (%) = [0.01/5.00] x 1000%
= 0.2%
e. Sample problem: Use the same burette to measure 43.82 ml
43.82 +/- 0.01ml
Absolute uncertainty = 0.01
Relative uncertainty (%) = (0.01/43.82] x 100%
= 0.20%
** Note that this is 10 x better than for the smaller volume above
Math operations with significant figures
Additional and subtraction- the absolute error (uncertainty) of the result is equal to the
largest absolute uncertainty of the quantities added/subtracted. (Simply stated: “line em
up and cut em off.”) for example;

1.256
0.2
9.31245
Sum = 10.96845 =11.0
Rounding off convention
3.2456 3 significant figures = 3.25
3.2450 3 significant figures= 3.24
3. 2449 3 significant figures= 3.24
Note that if the number is exactly half way between numbers (i.e. like
3.150 in the example above) the last digit to be kept is rounded up if odd and rounded down if
even.
Multiplication/division – the usual method is that the quotient/product should have the same
number of significant figures as the quantity multiplied/divided with the least number of
significant figures.
1- By strict interpretation, the answer should have same relative uncertainty as the factor with
largest relative uncertainty (i.e. the fewest significant digits). For example;
(5, 845) (98) = 572, 810 (calculator)
= 570, 000 (rounded to 2 significant figures)
= 573,000 (rounded to 3 significant figures)
Note that 98 almost has three significant figures (i.e. its nearly 100); its relative uncertainty is
approximately 1 part in 100.

Logarithms and antilogarithms:
1- A logarithm of “A” is a number “B” whose value is such that……..

A- 10B and log (A) = B (common log or log base 10)
B- eB and In (A) = B ( natural log)
2- we will work exclusively with common logs
3- logarithms are composed of a mantissa and a character. For example……………………..
log (523) = 2.718501= 2.719 (with appropriate significant figures)
2= the character
7185017 = the mantissa
Note that in scientific notation
523 = 5.23 x 102
Log 95.23) = 0.1785017 = the mantissa
Log (10+2) = 2 = the character
1. Significant figure rules for logs/antilogs

a. In a logarithm keep as many significant figures in the mantissa as there are in the original
number
b. In an antilogarithm, report as many significant figures as are to the right to the decimal in
the original number
c. For example
Log (1,293) = 3.1115985= 3.1116
Antilog (15.92) = 8.3176 x 10+15 = 8.3 x 10+15
Exact numbers have infinite significance
1- Exact numbers usually refer to a quantity that has a discrete amount (e.g. counted
items)
2- Defined numbers are exact (e.g. I centimeter = 10 millimeter is a define relationship).

3- Defined numbers are exact (e.g. 1 centimeter =10 millimeters is a defined
relationship
4- Pi (3.1415926535……) is considered to be an exact number
Elementary statistics
Introduction
This lecture introduces you to simple statistical terms, expressions and calculations relevant to
the analytical chemist.
Objectives
- State and explain all the simple statistical terms relevant to an analytical chemist
- Perform simple statistical calculations
- Distinguish between accuracy and precision
Definition of terms
1- Means (average)
The mean, arithmetic mean and average are synonymous terms that refer to the numerical value
obtained by dividing the sum of a set of replicate measurement by the number of individual
results in the set.
a. Of a sample (i.e. if N, the number of measurements is ≤ 20).
N
X ∑ X1
i=1
N
= (sum of all measurement)/number of measurements)
b. Of a population (i.e. if N> 20) ….

µ = population
= x
2. Median = middle result when the data are arranged by size. The median of a set is that result
about which all others are equally distributed, half being numerically greater and half being
numerically smaller. If the set consist of an odd number of measurements, selection of the
medium may be made directly, for a set containing an even number of measurements, the
average of the central pair is taken.
a. If the data is an odd numbered set, the median is the middle value.
b. If the data is an even numbered set, the median is the average of the middle two values.
An odd- numbered set;
2.9
2.6
2.4
2.3
2.2
Sum = 12.4
x
= 12.4/5 = 2.5
Medium = 2.4
An even- numbered set;

0.1000
0.0902
0.0886
0.0884
Sum = 0.3672
X = 0.3672/4 = 0.0918
Medium = (0.0902+0.886)/2 = 0.0894
3. Standard deviation
a. Of a sample (N≤20)
s=
√∑
N
s=¿ ¿¿¿¿
i=1

N–1
Where Xi represents an individual measurement, and X is the sample average
For example, given the following data set;
Data Deviation
2.3 |2.30−2.5| = |−0.2|
2.6 |2.6−2.5| = |+0.1|
2.2 |2.2−2.5| = ⌈−0.3⌉
2.4 |2.4−2.5| = |−0.1|
2.9 |2.9−2.5| = |+0.4|
S= √(−2)2 (0.1)2 +(-0.3)2+(-0.1)2+(0.4)2
S= 0.3
b. Of a population (N>20)
n
σ ∑ ¿¿)2
1=1
where μ is the population mean
4. Variance (S2)
∑ ¿¿)2
i=1
S 2
N= 1
5. Relative standard deviation (RSD) and coefficient of variation (CV)
a. RSD = s/ X
b. RSD can be expressed as a percentage parts per thousand, etc.
1). CV (%) (s/ X ) x 100% = CV is RSD expressed as %
2). RSD and CV usually give a clear picture of the data quality
3). Large RSD or CV implies poor quality

Accuracy versus precision
The term accuracy refers to the nearness of a measurement to its accepted value and is expressed
in terms of error. You should note the fundamental differences between this term and precision.
Accuracy involves a comparison with respect to a true or accepted value; in contrast, precision
compares a result with the best value of several measurement made in the same way.
The term precision is used to describe the producibility or repeatability of results. It can be
defined as the agreement between the numerical values of two or more measurement that have
been made in an identical fashion.
1- Accuracy is the closeness of a measurement to the true (or accepted) value
2- Accuracy is expressed by the absolute error or the relative error.
Absolute error (E) = Xi – Xt where Xt is the “true” value
Relative error (Er) = (Xi- Xt)/Xt] x 100% (expressed as a percentage)
Relative error (Er)= [ Xi- Xt)/ Xt] 1000ppt (expressed as a ppt)
Errors in experimental data

1. Determinate (or systematic) errors
a. Usually are related to improper experimental design or adjustment of experimental
apparatus
b. Sometimes related to a particular method
c. These errors systematically skew the observations
d. Determinate errors do not affect precision, and can in theory be eliminated
2. Indeterminate (or random) errors
a. Usually are related to insufficiently controlled variations in experimental conditions

b. Affect precision, but not accuracy
c. Cannot be eliminated, but can be treated (statistically)
Random error
It is impossible to perform a chemical analysis that is error free or without uncertainty.
Our goals are to minimize errors and to calculate the size of the errors
Titrations
Introduction
A titration is a process for determining the amount of a substance by measurement of the
quantity of a reagent required to react completely with that substance. Ordinarily, a titration is
accomplished by the controlled addition of a reagent of known concentration to a solution of the
substance until reaction between the two is judged to be complete; the volume of reagent is then
measured. Occasionally, it is convenient or necessary to add an excess of the reagent and then
determine the excess by back –titration with a second reagent of known concentration.
Objectives
 Define titration and identity the different titrimetric procedures
 Define all the terms related to titrimetry
The three types of titrimetric methods include;
1- Volumetric methods – measurement the volume of a solution (of known concentration)
required to react completely with an analyte
2- Gravimetric titrimetry – measuring the mass of a known reagent required to react
completely with an analyte.
3- Coulometric titrimetry- measuring the electrical current (amps) produced when a known
amount of reagent reacts completely with an analyte
In this lecture we shall mainly concern ourselves with volumetric methods since they are
equivalent in accuracy to gravimetric procedures and are more rapid and convenient; their use is
wide spread. These methods are among the most useful and accurate analytical techniques,
especially for millimole amounts of analyte. Manual titrations nowadays are used in situations
requiring high accuracy for relatively small numbers of samples. They are used for example to

calibrate or validate more routine instrumental methods. Automated titrations are useful when
large numbers of samples must be processed. A titration may be automated for instance by
means of a colour change or a pH change that activates a motor driven burette to stop delivery;
the volume delivered may then be registered on a digital counter. In this section, the types of
titrations that can be performed are described and the principles applicable to all are given,
including the requirements of a titration and standard solutions.
Titration principles
In a titration, the test substance (analyte) reacts with a reagent added as solution of known
concentration. This is referred to as a standard solution and it is generally added from a burette.
The added solution is called the titrant required to just completely react with the titrand
(analyte) is measured. In titrimetric analysis the reagent of known concentration is called titrant
and the substance being titrated is termed the titrand. Since the concentration is known and
since the reaction between the analyse and the reagent is known, the amount of analyst can be
calculated. The requirements of a titration are as follows;
 The reaction must be stoichiometric. That is there must be a well –defined and known
reaction between the analyte and the titrant. In the titration of acetic acid in vinegar with
sodium, hydroxide, for example, a well-defined reaction takes place. HC 3COOH (aq)
+NaOH(aq)- CH3COONa(aq) + H2O (1)
 The reaction should be rapid. Most ionic reactions, as above, are very rapid.
 There should be no side reactions and the reaction should be specific. If there are
interfering substance, these must be removed. In the above example, there should not be
other acids present.
 There should be a marked change in some property of the solution when the reaction in
complete. This may be a change in the colour of the solution or in some electrical or
other physical property of the solution. In the titration of acetic acid with sodium
hydroxide there is a marked increase in the pH of the solution when reaction is complete.
A colour change is usually brought about by addition of an indicator, whose colour is
dependent on the properties of the solution for example the pH.

 The point at which the equivalent or stoichiometric amount of titrant is added is called
the equivalence point. The point at which the reaction is observed to be complete is
called the end point, that is, when a change in some property of the solution is detected.
The end point should coincide with the equivalence point or be at a reproducible interval
from it.
 The reaction should be quantitative. That is, the equilibrium of the reaction should be far
to the right so that a sufficient sharp change will occur at the end point to obtain the
desired accuracy. If the equilibrium does not lie far to the right, then there will be a
gradual change in the property marking the end point (e.g. pH) and this will be difficult
to detect.
Terminology of volumetric titrimetry

Titration
Titration is the process in which the standard reagent is added to a solution of an
analyte until the reaction between the analyte and reagent is complete.
Equivalence point and End point
The equivalence point of a titration is a theoretical point that cannot be determined
experimentally. Instead, we can only estimate its position by observing some physical
change associated with the condition of equivalence. This change is called the end point
for titration.
Titration error
The difference between the observed end point and the true equivalence point in a
titration.
Standard solutions and primary standards
We have already defined a standard solution. A standard solution is generally used to perform
several analyses; since the quality of these analyses is directly related to the accuracy with which
the concentration of the reagent is known, the chemist ordinary expends considerable effort to
assure himself that the materials and methods used for preparation and standardization will lead
to a solution of accurately known concentration. The substance normally used to prepare a
standard solution is called a primary standard.

By definition, a primary standard is a substance that is analytically pure, and by dissolving a
known amount of it in a known volume of solvent, a solution of known concentration can be
prepared.
Requirements of a primary standard:
Certain properties are required if a substance is to serve as a primary standard;
 It must be of the highest purity and established methods should be available for
confirming its purity
 A primary standard substance should be stable. It should not be attacked by constitution
of the atmosphere.
 The compound should not be hygroscopic nor should it be efflorescent, otherwise,
drying and weighing would be difficult.
 A primary standard should be readily available and not too expensive
 Finally, it should have a reasonability high equivalent weight. The weight of a compound
required to standardize or prepare a solution of a given concentration increases directly
with its equivalent weight; since the relative error in weighing decreases with increasing
weight, a high equivalent weight will tend to minimize weighing errors.
Few substances meet or even approach these requirements, as a result, the number of good
primary standard substances available to the chemist is quite limited.
Stability of standards solutions

The concentration of the ideal standards solution should remain constant for months or years
after preparation. A few of the reagents used in volumetric analysis are stable for this length of
time. Many, however, require frequent re-standardisation and are used only when necessary.
Indicators.
Indicators are often added to analyte solution in order to give an observable
physical change (end point) at or near the equivalence point. In other wards indicator is a
compound having a physical property (usually color) that changes abruptly near the
equivalence point of a chemical reaction.
End Points in Volumetric Analysis

Detection of an end point involves the observation of some property of the solution
that change in a characteristic way at or near the equivalent point. The properties that
have been used for this purpose are numerous and varied; they include:
1. Color due to the reagent, the substance being determined, or an indicator
substance.
2. Turbidity changes resulting from the formation or disappearance of solid phase.
3. Electric conductivity of the solution.
4. Electric potential between a pair of electrodes immersed in the solution.
5. Refractive index of the solution.
6. Temperature of the solution.
7. Electric current passing through the solution
Review of volumetric calculations

Introduction
Quite often you will be confronted with a variety of questions that do involve calculations based
on determination of volumes. This lecture is therefore intended to make you get the basics as far
as these calculations are concerned.
Objectives
- Work out simple volumetric calculations
- Classify volumetric methods
Mole calculations
Mole of species X= [ number of grams of X] / [ Molar Mass of X]
Moles of X = [ Volume in litres] [ molarity]
For dilutions
([volume] [ molarity before dilution = ([ volume] [molarity]) (after dilution)
Activity
 Describe the preparation of 900.0mL of 0.450M KOH from a 50.0% stock KOH solution
(specific gravity of the stock solution = 1.505).

Classification of volumetric methods
There are four general classes of volumetric methods
1- Acid –base Titrimetry: Many compounds, both inorganic and organic, are either, acids or
based and can be titrated with a standard solution of a strong base or a strong acid. The end
points of these titration are easy to detect, either by means of an indicator or by following
the change in pH with a pH meter. The acidity and basicity of many organic acids and
bases can be enhanced by titration in a non-aqueous solvent. The result is a sharper end
point, and weaker acids and bases can be titrated.
2- Precipitation. In the case of precipitation, the titrate forms an insoluble product with the
analyst. An example is the titration of chloride ion with silver nitrate solution. Again,
indicators used to detect end point or the potential of the solution can be monitored
electrically.
3- Complexometric. In complexometric titrations, the titrant is a complexing agent and
forms a water-soluble complex with the analyte a metal ion. The titrant is often a chelating
agent. The reverse titrant may be carried out also. Ethylenediaminetetraacetic acid
(EDTA)-will react a large number of elements and the reactions can be controlled by
adjustment of the pH. Indicators can be used for form a highly coloured complex with the
metal ion.
4- Reduction – oxidation. These ‘redox’ titrations involve the titration of an oxidizing agent
with a reducing agent, or vice versa. An oxidizing agent gains electron and reducing agent
loses electrons in a reaction between them. There must be a sufficiently large difference
between the oxidizing and reducing capabilities of these agents for the reactions to go to
completion and give a change at end point, that is one should be a fairly strong oxidizing
agent (strong tendency to gain electrons) and the other fairly strong reducing agent (strong
tendency to lose electrons). Appropriate indicators can be used for these titrations or
various electrometric means can be employed to detect the end point.
These different types of titrations and means of detecting their end points will be treated
separately in succeeding lectures.
Molarity volumetric calculations

We shall use morality through the majority of the text for volumetric calculations. Another
useful concentration unit for volumetric calculations is normally using the concept of equivalents
and weights in place of moles and formula weights. Normal concentration depends on the
particular reaction, and the reaction should be specific. We reviewed some of the ways of
expressing concentration earlier in the course.
The goal of every titration is the addition of standard solution in an amount that is chemically,
equivalent to the substance with which it reacts. The condition is achieved at the equivalent
point. For example, the equivalent point in the titration of sodium chloride with silver nitrate is
attained when exactly one formula weight of silver ion has been introduced for each formula
weight of chloride ion present in the sample. In the titration of sulphuric acid with sodium
hydroxide, the equivalent point occurs when two formula weights of the latter have been
introduced for each formula weight of the former.
The equivalence point in a titration is a theoretical concept. In actual fact we can estimate, its
position only by observing physical changes associated with it in the solution.
These changes manifest themselves at the end point of the titration. It is to be hoped that the
volume difference between the end point and equivalence point will be small. Differences do
arise, however, owing to inadequacies in the physical changes and out of ability to observe them.
This results in an analytical error, called a titration error as we shall see later.
One of the common methods of end-point detection in volumetric analysis involves the use of a
supplementary chemical compound that exhibits a change in colour as a result of concentration
changes occurring near the equivalence point. Such a substance is called an indicator and will be
discussed at length in the next lecture.
To be suitable for a volumetric analysis, a chemical reaction should meet certain requirements.
 The reaction ought to be rapid. Normally, titration involves addition of the reagent in small
increments and observation of the solution for the end point. If the chemical reaction is
slow, a period of waiting must follow each addition and the whole process become
prohibitively time-consuming and tedious.

 The reaction should proceed reasonably for forward completion. As we shall presently
show satisfactory end points for most titration require this second condition.
 The reaction must be such that it can be described by a balanced chemical equation
otherwise, the weight of the sought for substance cannot be calculated directly from the
volumetric data. This requirement implies that absence of side reactions between the
reagent and the unknown or other constituents of the solution
 There must be available a method for detecting the equivalence point in the reactions, that
is a satisfactory end point is required.
Not all volumetric reactions currently in use meet these requirements perfectly the most widely
accepted procedures however, are all founded on reactions that closely, approach them.
Neutralization titrations- an overviews of titration curves

Introduction
End points in neutralization titration are ordinary based upon the abrupt change in pH that occurs
in the vicinity of the equivalence point. The pH range over which such change is observed
depends upon the nature and concentration for the substance titrated as well as the titrant. Proper
selection of an indicator for any case requires knowledge of the general features of the titration
curve for the system. Thus, we need to consider how such curves are derived. In this lecture
therefore, we will examine titration and titration curves from the reactions of strong acids with
strong bases. We will also consider the utilization of acid –base indicators and the criteria for
their selection as end point indicators. Buffers will be defined, and buffer calculations will be
considered. The titrations and titration curves of weak acids with strong bases will also be
considered.Titration of weak based with strong acids will be considered. Lastly, calculation of
buffer composition utilizing alpha values will be examined.
Objectives
 Define a titration curve
 Identify the different types of titration curves
 Derive titration curves for acid-base reactions
 Define acid –base indicators and explain how they work

 Explain how a good indicator can be chosen
A titration curve is a plot of reagent volume against some function of the analyte concentration
1- Volume of added reagent is generally plotted on the axis
2- The measured parameter that is a function of analyte concentration is plotted on the Y-
axis
There are two general types of titration curves.
1- Sigmoidal curve – this is a ‘z’ or ‘s’ shaped curve where the Y- axis is a p- function of the
analyte (or the reagent reaction with the analyte during titration) or the potential of an ion-
specific electrode.
p- function
Volume of Reagent
a. The equivalence point is observed in the middle of the ‘middle’ segment of the ‘z’ or “s”.
b. A large number of measurements are made near and surrounding the equivalence point.
2. Linear-segment curve- curve generally consisting of two-line segment that interact at an
angle.
Volume of Reagent
Measured property
a. Measurements are often made well always from the equivalence point (where the reaction is
nearly complete) and the lines are extrapolated to intersection
b. The equivalence point is generally associated with the intersection of the line segments
3. The vast majority of titrations follow a sigmoidal curve, we will deal exclusively with that
type.
Typical titration strong acid (HCI) titrated with strong base (NaOH)
We have already seen that strong acids and strong bases ionize with 100% efficiency in aqueous
solution.
HA (aq) …………… H3O+ (aq)+ A (aq)

Metal OH (aq) …. Metal+ (aq) + OH(aq)
The net reaction of strong acids with strong bases is the reaction of a hydronium ion with a
hydroxide ion to form water.
H3O+ (aq) + OH- (aq) →H2O(aq)
Consider a hypothetical titration of a 50.000ml aliquot of 0.10MHCI with 0.10M NaOH.
HCl (aq) + NaOH (aq) → H2O (1) + NaCI (aq)
1. The progress of the titration can be followed as a function of pH or pOH
pOH pH
pH
Volume of Reagent
2. Since the acid and base have the same concentration. It is correctly assumed that
50.00ml of NaOH solution will be required to reach equivalence.
pH
0 10 20 30 40 50
Volume of Reagent (mL)
a. Note that during titration, little change occurs up to about 40.0ml. pH remains
constant, despite the fact that a lot of base has been added.
b. Near the equivalence point, tiny volumes of NaOH are added.
c. Note that from 49.99ml to 50.00 ml a pH 7.0 jump occurred
1) From 50.00ml to 50.01 ml a pH 7.0 to pH 9.0 jump occurred.
d. Past the equivalence point, large additional volumes of NaOH make little differences
in pH. The pH asymptotically approaches the pH of 0.10 M NaOH.
e. Note that the titration can be plotted as a function of pH or pOH

f. Indicators must change colour abruptly in the equivalence region to be of use
(typically 1-2 pH units). In this case, any indicators that changes +/-2 pH units of 7
will work
Titration curves of strong acids titrated with strong bases are divided into domains
1- Before equivalence
2- At equivalence
3- After equivalence
Before equivalence
1- Initially before any base is added to the acid sample the (H3O+) total = CHA+ (H3O+] water
2- If the CHA is greater than 10-6 M, the (H3O+) water can be ignored
3- As strong base is added by prior to equivalence, [H 3O+] is consumed. The remaining [H3O-]
is calculated as; -
[H3O1+] = Total ≠ mole H3O1+ initially - ≠ moles H3O1+ Reacted

(Total volume) litres
= Total ≠ mole H3O1+ initially - ≠ moles H3O1+ added

= VHA CHA – V base Cbase (Assuming a monohydrous bases)

At equivalence
1- The acid and base have reacted at the stoichiometric ratio

2- The (H3O+] = [OH) = √ Kw = 1 x 10-7 M
3- The pH = 7 at equivalence
Beyond equivalence
1- All the acid is consumed; only base is present

2- The amount of base is calculated from the excess added beyond equivalence

C base = [ OH1-]
[OH1-] = Total ≠ moles OH1- added - ≠ moles OH1- reacted

[Total volume] litres
= Total ≠ moles OH1- added - ≠ moles OH1-initially

[Total volume]litres
VHA CHA – V base Cbase (Assuming a monohdrous bases)

(Total volume)litres
Kw
(H3O1+] =
¿¿
From which the pH can be calculated
Titration concentrations and titration curves of strong bases with strong acid are calculated in
similar fashion.
Note that;
1- If the Cacid is greater than 10-6 M, we have assumed that the water contribution to the
hydronium ion concentration can be ignored.
2- If the C acid is less than 10-18 M, you can also assume that the water is primarily
responsible for the hydronium ion concentration and that the added acid is insignificant
3- Only when the Cacid is between 10-8 −¿ 10-6 M must the water contribution to the hydronium
ion concentration be considered.
Titration curves for weak acids titrated with a strong base
Acetic acid titrated with NaOH
 Acetic acid is a monoprotic acid (pKa= 4.757).

 NaOH is a monohydroxy, strong base
 Titration of acetic acid with NaOH follows a curve similar in shape to the strong acid –
strong base titration curve, but the equivalence point is not a pH
 Shown below is a titration curve for 0.100 M acetic acid titration with 0.100M NaOH

12
10 Equivalence point
pH
8
6
pK
4
During the titration and in the generation of a titration curve, four regions will be considered
0 10 20 30 40 50
1- No NaOH added (i.e. 0.10M acetic acid)
2- NaOH added, but Volume of NaOH (mL)
before equivalence has been reached
3- At the equivalence point (i.e. 0.10M acetate ion)
4- After equivalence
 No NaOH added
1- (H2O-] is calculated from the Ka of acetic acid
Ka = [H3O1+] [Ac1-] = X2
[ HAc] CHAc – X
Re arrangement and assuming X << CHAC

X = H3C1+] = √ K aCHAC
a. In using these equations, check the assumptions made that allow use of Ka or the
Henderson – Hasselbalch. They are
1)- Water equilibrium contribution are negligible
2) CNaAC and C HAC >> [H3O+] and [OH-]
At equivalence
1- At equivalence, that HAC and NaOH have reacted at the stoichiometric ratio.
Number of moles of HAC initially present= number of moles of NaOH added.
3. The solution at the equivalence point is identified to dissolving sodium acetate (NaAC) in
water. The [H3O+] may be calculated from the base hydrolysis of AC.
AC1-+ H2O HAc + OH1-

Kw
Ka = [ HAc] [OH1-] = = 1.00 x 10-14 = 5.71 x 10-10
Ka
[Ac1-] 1.75 x 10-5

Ka = [X] [X]
[CNaAc-X]
Ka = [OH1-] = √ K b [ CNAAC]
a. Note that X is assumed to be << NaAC. This assumption must be checked

b. If the assumption is not true, the quadratic formula must be used to solve for X
 Beyond equivalence
1. Beyond equivalence all the HAC is consumed and the presences of excess OH prevents the
base hydrolysis of the AC
2. The concentrations of the excess OH is calculated from the reacted volumes and used to
calculate [H3O+]and pH.
[OH1-] = total ≠ moles OH1- added-≠ moles HAC initially

Total volume (in liters)
General characteristics of weak acid titration with strong bases
1- If the concentration of acid are too low, you cannot ignore the water contribution to [H 2O1-]
and [ OH]
2- Low acid concentration decreases the magnitude of the pH change at the equivalence
point, limiting the selection of endpoint indicator. Conversely, the higher the acid
concentration, the larger the pH change around the equivalence point.
3- As Ka gets smaller, the pH change at equivalence gets smaller. Generally, the smaller Ka
gets the more concentration the solutions must be. Acids with Ka below 10 -6 -10-7M are
nearly impossible to titrate easily with a burette and typically endpoint indicator.
Titration curves for weak bases titrated with a strong acid
Titration of weak bases with strong acids are “mirror images” of the weak acid titration already
discussed.
Shown below is a typical titration curve
pKb
pH
Equivalence point

Volume of HCL (mL)
For the sake of discussion, assume cyanide ion, CN- from NaCN, is being titrated with HCl. The
titration curve is divided into regions similar to the acid titrations
1. No HCI added
2. HCl added, but before equivalence
3. At equivalence
4. After equivalence
 No HCl added region
1. [OH] is calculated from the Kb expression
Kb = [HCN][OH1-]
[ CN1-]
Kb = [HCN][OH1-]
[ CNaCN - X]
X= [OH1-] = √ K b [CNacn]
2. Once [ OH-] is calculated, [H3O+] and pH is calculated.
HCl added but before equivalence point:

1. The solution is a buffer consisting of HCN and CN-
2. The concentration is each species is calculated from the added volumes and
substituted into the Henderson – Hasselbach equation (or Ka for HCN)
[ CN1-] = CNACN = total≠ moles NaCN initially-≠ moles HCL added

Total volume (in litres)
[HCN] = CHCN = total≠ moles HCI added
C NaCN
pH = Ka + log ⌈ ⌉
C HCN

a. Note again, the assumptions are made about ignoring waters contributions to [OH]
and [H3O-]. These assumptions must be checked.
b. Also, it is assumed that [OH] and H3O+] are << CNaCN and CHCN. This also must be
checked
At the equivalence point

1. All the CN- has been converted to HCN. The solution is the same as an HCN solution.
[HCN] = CHCN = total≠ moles HCI added
X = H3O1+] √ K a [CHCN]
a) Note the same sets of assumptions to be checked.
 After the equivalence point

1- The pH is determined by the amount of acid added in excess to the amount of CN -
initially present.
[H3O+] = total≠ moles HCI added-≠ moles CN-1 initially
a. Note yet again the same sets of assumptions to be checked
Acid – base indicators
Acid- base indicators, (pH indicators) are weak, organic acids or weak organic bases that change
colour as a function of ionization state.
Acid- base indicators of two types have different ionization equilibria
1- Acid type indicators; HIn + H2O H3O+ + In- (In= indicators)

One colour different colour
2- Base –type indicators In + H2O OH- + HIn+
One colour different colour

As the pH changes, each equilibrium above shifts in response, producing a colour
Human visual perception only responds to dramatic colour changes. Changes of less than 10%
usually are not visible. Thus, the molar concentration of the indicator’s species must constitute
approximately 90% of the indicators before the colour changes are seen clearly.
1- To see the in colour [In1-] ≥ 10

[HIn]
2- To see the Hln colour [In1-] ≤ 0.10

[HIn]
3- Acid- base indicators (like any ionizable molecule) are 50% ionized at the pKa.
4- At 1 pH unit above the pKa 90% of the ionizable indicators is in its basic form
5- At 1 pH unit below the pike 90% of the ionizable indicators in its acid form
6- Thus, indicators show a full colour transition+/- 1 pH unit of the pK a and indicators are
generally selected based upon the closeness of their pKa to the endpoint pH.
Variables affecting acid- base indicator behavior include;
1- Ionic strength (changes Ka shifts equilibrium)

2- Temperature
3- Solvent and solvent polarity (especially organic solvent which may shift color transitions
several pH units)
4- Colloidal particulates may interfere through surface adsorption of the indicator
Table 4: Some important acid-base indicators
Colour change
Common name Transition Acid Base Indicator type
range (pH)
Methyl violet 0.5-1.5 Yellow Blue
Thymol blue 1.2 -2.8 Red Yellow 2
8.0 – 9.6 Yellow Blue
Methyl yellow 2.9 – 4.0 red Yellow 3
Methyl orange 3.1- 4.4 red Yellow 3
Bromocresol 3.8- 5.4 Yellow Blue 2
green
Methyl red 4.2 – 6.3 red Yellow 3

Chlorophenol red 4.8- 6.4 Yellow Red 2
Bromothymol 6.0- 7.6 Yellow Blue 2
blue
Phenol red 6.4 -8.0 Yellow Red 2
Phenol red 6.4 - 8.0 yellow Red 2
Neutral red 6.8-8.0 Red Yellow-
orange
Cresol purple 7.4-9.0 Yellow Purple 2
1.2-2.8 Red Yellow 1
Phenolphthalein 8.0 -9.6 Colorless Red 1
Thymolphthalein 9.3-10.5 Colorless Blue 1
Alizarin yellow 10.1-12.0 colorless Violet 3
Phthalein indicators
Most phthalein indicators are colourless in moderately acidic solutions and exhibit a variety for
colours in alkaline media. In strongly alkaline solutions their colours tend to fade slowly, which
is an inconvenience in some application. As a group, the phthalein’s are sparingly soluble in
water but quite soluble in alcohol, the latter is the preferred solvent in preparing solutions of
these indicators. The best-known example of phthalein indicators is phenolphthalein, whose
structures may be representing as…
Structure of Phenolphthaleine
Choice of indicators for strong acid –strong base titration

1. If concentrations of acid and base are 0.1M or higher, it does not make much difference.
The large endpoint transition spans the colour transition range of almost all indicators
2. If concentration drop significantly below 0.1M an indicator whose pKa is as close as
possible to pH 7.0 +/- is best.
3. If concentration of acid and base drop too low, (i.e. the endpoint transition spans less than
two pH units) no indicators will work very well.
It is important to choose an indicator whose pH range coincides with the pH resultant solution at
equivalent point.
Titrating poly- functional acids and bases (complexometric titrations)
Introduction
Poly-functional (polyprotic) acid contains more than one ionizable hydrogen atoms. This would
include solutions such as a phosphoric acid, carbonic acid, citric acid, ethylenediaminetracetic
acid (EDTA), maleic acid, malic acid, sulfurous acid and others such as the H2M system.
Objectives
By the end of the lecture, you should be able to; -
 Define a poly-functional or polyprotic acid

 Derive expressions that can be used to calculate fractional amounts of different species in
solution
 Use the phosphoric acid and EDTA models to explain the behavior of polyprotic substance
in aqueous solution
 Discussion of the role of EDTA in metal ion complex formation and its use in estimation in
of the relevant amounts of metal in solution
 Derive EDTA titration curves
 Define metallochromic indicators explain how they are commonly employed in titrimetric
procedures
 Discuss the titrimetric methods that employe EDTA

In order to understand clearly the compositional changes that occur in the course of a titration
involving a polybasic acid, it is advisable to plot the relative amount of the free acid as well as
each of its anions as a function of the pH of the solution.
Polyhydroxy bases are treated essentially the same as polyprotic acids. We will leave polyprotic
bases for future courses.
We will use a few of these systems to describe the behavior of polyfunctional acids but first, let
us look at the dibasic acid system.
The dibasic acid system (H2M)
For such a system the following equilibria exit
H2M + H2O = H3O- – MH- for which K1 = [ H3O-] [HM-]

[H2M]
Then
HM + H2O = H3O- + M2- for which K2 = [ H3O-] [M2]

[HM]
If we define the so-called α values for each of the anion –containing species, as fractions of the
total concentration represented by each species and C1 as the sum of the concentrations of all the
species containing the ligand, then;
C1 = [H2M] – [HM]- (M2)
α0 = [ H2M]
C1
α1 = [ H2M]
C1
α 2= [ M2]
C1
Where α0 + α1 + α2 = 1

We can readily express α0 + α1 and α2 in terms of [H3O]K1 and K2. Thus, arrangement of the
dissociation – constant expressing gives.
[ HM] = K1[H2M]
[H3O]
[ HM] = K1 K2 [H2M]
[H3O]2
After substituting these quantities, the mass- balance equations becomes.
[H2M] - K1 K2 [H2M] + K1 K2 [H2M]

[H3O-] [H3O]2
Which can be converted to;
[ H2M] = C1 [H3O-]2
[H3O+]2 + K1 [H3O-] + K1K2
Substituting this value for [H2M] into the equation defining α0 we obtain
α0 = [H3O-]2
[H3O+]2 + K1 [H3O-] + K1K2
By similar treatment, it is easily shown that
α1 = K1 [H3O-]
[H3O+]2 + K1 [H3O-] + K1K2
α2 = K1 K2
[H3O+]2 + K1 [H3O-] + K1K2
Note that the denominators is the same for each expression and calculation α - values at any
desired pH is relatively simple. Furthermore, the equations illustrate that the fractional amount of
each species in dependent upon pH but independent of the total concentration. C1. The same
treatment can be applied to other systems as will be shown hereunder
The Phosphoric Acid Model
Phosphoric acid has three ionisable hydrogens

First ionisable
H2PO4 + H2O H2O1+ + H2 PO2
K2 = [ H3 O+] [H2PO4-] = 7.11 x 10-3

[H3PO4]
Second ionization
H2PO4- + H2O H3O+ HPO42-
K2 = [ H3 O+] [H2PO4-] = 6.32 x 10-3

[H3PO4]
Third ionization
HPO42- −¿ H2O H3O+ + PO43-
K2 = [ H3 O1+] [PO43-] = 4.5 x 10-3

[HPO42-]
1. Note that each Ka differs by about 10-4 – 10-5 smaller than the previous. The reason for this
difference is that it is harder to pull additional protons away from a species that is more
highly negatively charged.
2. A rigorous solution for the concentration of all the phosphate –containing species at a given
pH during titration would involve.
a. Seven (7) unknowns - [H3O1-], [OH1-] [H3PO4], [H2PO41-], [HP42-], [PO43-] and [Na1-]
b. Solving seven (7) simultaneous equations. These equations would be derived from;-
1) Kw
2) K1-
3) K2-
4) K3-
5) Mass balance for NaOH

[Na] = number of moles of NaOH added/total volume
(6) Charge balance
[H3O2] [Na] + [OH1-] – [H2PO4] + 2[HPO42] 3[PO43-] 3 [PO43]
Mass balance for phosphate –containing species
[H2PO4] + [ H2PO41-] [ PO43]
This is a hopelessly complicated system
To simplify calculation intelligent approximations must be made
Plots of alpha values versus pH allow quick approximation and rapid solution to these kinds of
calculations.
Alpha values versus pH plots
The curve is
constructed by calculating the “crossover” points C1 C2and C3
1. At C1 both [H3PO4] and [H2PO4] are preset at 0.5 alpha, equal mole numbers and 50% each,
of the total phosphate. No significant [PO43] and [HPO42] are present.
2. This corresponds to pK1 (substitute (H3PO4] into the K1 expression since [H3PO4] equal
[H3PO4] equal [H2PO4] at C1, they cancel in the K1 expression and K1 = [H3O]

3. Note that the other phosphorus containing species are essentially zero in concentration at C.
These other species [HPO42-] and [PO43-]) need not be considered around C1
4. Similar arguments hold for the C2 and C3 and crossover points
Activity
 Calculate the concentration of all the phosphate containing species in a 0.50M phosphoric
acid solution at pH 1.5
For more situations the crossover point and associated Ka nearest the given pH are assumed to
predominate provided the other crossover points are not closed than 12 pH units.
If the crossover points are too close together to ignore the concentration of the other chemical
species, the concentration of all species can be calculated a different way using alpha values.
α0 = [H3PO4]
[H3PO4]+[H2PO41-] + [HPO42-] + [PO43-]
α1 = [H2PO41-]
[H3PO4]+[H2PO41-] + [HPO42-] + [PO43-]
α2 = [HPO42-]
[H3PO4]+[H2PO41-] + [HPO42-] + [PO43-]
α3= [HPO43-]
[H3PO4]+[H2PO41-] + [HPO42-] + [PO43-]
Each alpha values can be expressed by equations containing only K a’s and [H3O-] This is a
accomplished by solving for all of the phosphate –containing species in terms of one species
(using the Ka expression much like what was done in the multiple equilibria calculations of
previous chapters) and substituting into the alpha expression above.

α0 = [H3O1+]3
[H3O1+] 3+[H2O1+]2 + K1 + [H3O1+] K1 K2 + K1 K2 K3
α1 = K1[H3O1+]2
[H3O1+]3 +[H2O1+]2 + K1+ [H3O1+] + K1K2 + K1K2K3
α2 = K1K2 [H3O1+]
[H3O1+] 3+[H2O1+]2 + K1 + [H3O1+] K1 K2 + K1 K2 K3
α3 = K1K2K3
[H3O1+]3 +[H2O1+]2 + K1+ [H3O1+] + K1K2 + K1K2K3
To calculate the concentration of any phosphate –containing species, simply multiply its
calculated alpha value of the species times the total phosphate concentration;
(phosphate -containing species] =0 expenses C total
Activity
 Calculate the concentration of phosphoric acid, H 3PO4 in a 0.30 M H3PO4 solution at pH
5.00.
 Read about the EDTA complexes and compare the EDTA model with the previous model.
Complexes of EDTA and metal ions

One of the valuable properties of EDTA as a titration is that it combines with metal ions in a 1:1
ratio regardless of the charge on the cation. In moderately acidic solution, these reactions can be
formulated as;
M2- + H2Y2- = MY2- + 2H-
M3+−¿ H2Y2- = MY- + 2H-
M2+ - H2Y2- = MY + 2H
Thus, it is apparent that reactions performed in neutral or basic solutions are best written as;
Ma- - HY 3- = MYm-4 + H+

EDTA is remarkable from the standpoint of the high stability of its metal complexes. All cations
react at least to some extent, with the exception of the alkali metals, the complexes formed are
sufficiently stable to form the basis for volumetric analysis. This great stability arises from the
several complexing groups within the molecule, giving rise to structures that effectively surround
and isolate the cation.
Formation and stability of metal EDTA chelates

EDTA forms stable complexes with a wide variety of metal ions. However, inspection of metal-
ion EDTA equilibrium reveals that the extent of complex formation will be dependent upon the
pH of the environment. Thus, an alkaline medium is needed for titration involving cations such
as calcium and magnesium, which form weak complex with EDTA. On the other hand, titration
can be performed successfully in moderately acidic solution with cations that form more stable
complexes, such as zinc and nickel.
Because of this pH dependence EDTA titrations are generally carried out in solution that are
buffered to a constant and predetermined pH. Derivations of titration curves under these
circumstances require knowledge of both the formation constant for the complex and the pH.
In the derivation of EDTA titration curves for buffered solutions, it is convenient to employ the
term α4 which we can define as;
4−¿
Y
𝑎4 ¿
C1
In this expression, C1 is the total concentration of uncompleted EDTA that is
C1 = [Y4-] + [HY3-] + [H2Y2+] + H2Y] + [H2Y]
Thus C4, represents the fraction of the total in complexed reagent that is in the form of Y4
C4 = K1K2K3 K4
[H-]4 + K1 [H+] + K1K3 [H-]2 + K1K2K3 [H+] + K1K2K3K4

NOTE:
It is thus, possible to plot a graph of α – values against the pH of the solution as in the case of
the phosphoric acid model.
In the following table α4 values for EDTA at several pH level are tabulated
Table 8: Values for α4 v for EDTA in solutions of various pH

pH α4 pH α4
2.0 3.7 x 10-4 7.0 4.8 x 10-4
3.0 2.5 x 10-11 8.0 5.4 x 10-3
4.0 3.6 x 10-9 9.0 5.2 x10-2
5.0 3.5 x 10-7 10.0 3.5 x 10-1
6.0 2.2 x 10-5 12.0 9.8 x 10-1
Thus, for the equilibrium

M= Y2 = MYm+
A formulation constant expression can be written as;
KW = [ MY m-4p]
[ M n+] [Y-4]
But α4 = [Y4-]
C1
This implies the [Y4-] = α4C1= meaning that;
Kw= [ MY(n-4+]
[ Mn+] [Y-4-]
The above expression can be re-arranged do yield;

α 4 Kmy = [ MY (n-4)+]
[ MN+] C1

= K1my
Where K’my is the product of the formation constant for the complex MY and α4. K’my is
called a conditional or effective formation constant and is clearly dependent upon pH just like α4.
As we shall show, conditional constant provides a simple means by which the equilibrium
concentrations of metal and complex can be calculated at any point in a titration curve. Note
that the expression for the conditional constant differs from that of the formation constant only
in the C1 replaces the equilibrium concentration of the completely dissociated anion [ Y 4-]. The
differences is significant, however, because it is much easier to determine a value for C1 than for
[Y-4] at any point in the titration.
Table 7: Formation constant for EDTA complexes
Cation Kmy LogKmy Cation Kmy LogKmy
Ag+ 2 x 107 7.3 Cu2+ 6.3 x 1018 18.80
Mg2- 4.9 x 108 8.69 Zn2+ 3.2 x1016 16.50
Ca2- 5.0 x 1010 10.70 Cd2+ 2.9 x 1016 16.46
Sr2 4.3 x 108 8.63 Hg2+ 6.3 x 1021 21.80
Ba2- 5.8 x 10- 7.76 Pb2+ 1.1 x 1018 18.04
Mn2+ 6.2 x1013 13.79 Al3+ 1.3 x 1016 16.13
Fe2+ 2.1 x1014 13.79 Fe2+ 1 x 1025 25.1
C02- 2.0 x 1016 14.33 V3- S x 1025 25.9
N12+ 4.2 x 1018 16.31 Th4- 2 X1023 23.2
The table lists formation constant K my for a variety of EDTA complexes. Note that the constant
refers to the equilibrium involving the species Y+4 with the metal ion.
Titration curves for complex formation reactions

The general approach to derivation of a titration curve for metal – ion EDTA reaction does not
differ fundamentally from that used for precipitation or neutralization titrations. Here, however,
it is necessary to use several equilibria. As a result, the computational details are somewhat
greater than in the earlier examples.
Activity
 Derive a titration curve for 50.0ml of 0.01M Ca 2- with 0.01M EDTA in a solution buffered
to a PH of 10.0
Calculation of conditions constant

The conditional formation constant for the calcium – EDTA complex at pH 10 can be obtained
from the formation constant of the complex and the α4 value of EDTA at pH 10 is also given.
Thus,
Kcay = Kacyα4 = 5.0 x 1010 x 0.35 = 1.75 x 1010
Pre- equivalence point values of pCa

The molar concentration of Ca2+ will be equal to the sum of the contribution of the untitrated
excess of the ion and that which results from dissociation of the complex which will be equal to
C1. It is reasonable to assume that the latter is small with respect to the former, thus for example
after the addition of 25.0 ml of reagent
[Ca2-] = 50.0 x 0.01 – 250 x 0.01 + C1 ≅ 3.33 x 10-3
and
p Ca = 2.48
Equivalence point pCa
Here we have 0.005M solution of CaY2 and Ca2 ions are present only from dissociation of this
complex. It is evident that the calcium ion concentration must be identical to the sum of the
concentration of the uncomplexed EDTA ions, CI. Thus,
[ Ca2-] = C1
[CaY2-] = 0.0050 – [Ca2-] ≅ 0.00590
The conditional formation constant for CaY2- at pH 10 is formulated as
[CaY2-] = 1.75 x102-
[ Ca2-] Cr
Thus, upon substitution
0.0050 = 1.75 x 1010

[Ca2+] 2
[ Ca2-] = 5.35 x 10-7

pCa = 6.27

Post equivalence point pCa
Beyond the equivalence point, molar concentration of CaY2- and EDTA are readily obtained. For
example, after addition of 60 ml reagent.
[ CaY2-] = 50 x 0.0100 = 4.54 x 10-3
110
[ EDTA] = 10 x 0.0100 = 9.1 x 10-4
As an approximation, we may write

[ CaY2-] = 4.5 x 10-3 – [ Ca2+] ≅ 4.5 x 10-3
C1 = 9.1 x 10-4 + [ Ca2-] ≅ 9.1 x 10-4
And
4.54 x 10-3 = 1.75 x 10 = Kcay
[ Ca2+] x 9.1 x 10-4
[Ca2-] = 2.85 x 10-10

pCa = 9.54
It is possible to sketch a titration curves for calcium ion in solution buffered to various pH
levels. End points can be achieved only if the pH of the solutions is maintained at about 8 or
greater. For cations with higher stability constants, however, good end points are realized even in
acidic solutions.
End point of EDTA titrations

Metal –ion indicators
A number of metal-ion indicators have been developed for use in complexometric titrations with
EDTA and other chelating reagents. These indicators are commonly referred to as
metallochromic indicators. In general, these indicators are organic dyes that form coloured
chelates with several metal ions in a pM range that is characteristic of the particular metal ion
and dye.

Most metal –ion indicators will also bond with protons to give species that impart colours to
solutions resembling those of the metal complexes. Thus, materials functions as acid base
indicators as well and will be useful as indicators for metal ions only in pH ranges in which
competition with the proton does not occur to a significant extent. Examples of such indicators
include eriochrome black T. calcon and murexide.
The metal complexes of eriochrome black T are generally red, thus in order to observe a color
change with this indicator, it is necessary to adjust the pH to 7 or above so that the blue form of
the indicators Hln2- predominates. The end point reaction is then.
Hln2- −¿ M2- = Mln + H+

Blue red
The resulting coloured complex is probably tridentate, the bonding involving the two phenolic
oxygen atoms and one of the nitrogen atoms of the azo group. The colour of this complex is
similar in appearance of the protonated species, H2In.
Eriochrome black T forms red complexes with more than two dozen different metal ions, but
with only certain of these cations are the stabilities of the complexes appropriate for endpoint
detection. To be suitable for a titration with EDTA the formation constant of the metal indicators
complex should be less than tenth that of the metal EDTA complex. Otherwise a premature end
point will be observed. On the other hand, if this ration becomes too small, as is the case with
calcium ion, late end points are observed. The applicability of a given indicators to an EDTA
titration can be determined from the change in pM in the equivalent point region provided the
formation constant for the metal- indicators complex is known.
Titration methods employing EDTA

Several procedures are employed in the application of EDTA to volumetric analysis. The most
common of these are considered in the following paragraphs.
Direct titration procedure

There are about 25 metals that can be determined by direct titration with EDTA using metal
indicators for end-point detection.
Direct titration procedures are limited to those reactions for which an end point can be devised
and to those metal ions that react rapidly with EDTA. When direct methods fail, however, it is
often possible to achieve an analysis employing back-titration or displacement titration methods.
Back titrations
Back –titration procedures are useful for the analysis of metallic ions that form very stable
complexes with EDTA and for which a satisfactory indicator is not available. In such an analysis
the excess EDTA is determined by back- titration with a standard magnesium solution, using
eriochrome black T as the indicator. The metal EDTA complex must be more stable that the
magnesium EDTA complex. Otherwise, the back –titrant would displace the metal ion.
This technique is also useful for the titration of metals in the presence of anions that form
slightly soluble precipitates with the cation under the conditions of the analysis, the presence of
EDTA prevents their precipitation.
Displacement titrations
In displacement titrations an excess of a solution containing EDTA in the form of a magnesium

or zinc complex is introduced; if the metal ions form a more stable complex than the of
magnesium or zinc, the following reactions occurs.
MgY2- + M2- = MY2- + Mg2-
The liberated magnesium is then titrated with a standard EDTA solution. This technique is useful
where no satisfactory indicators is available for the metal ion being determined.
Scope of complexometric titrations
Complexometric titrations with EDTA have been reported for the analysis of nearly at the
metallic ions. Because of the tendency of the reagents to complex most cations,EDTA would

appear at first glance to be totally lacking in specificity. In fact, however, considerable control
over the behavior of this reagent and other chelating agents as well can be achieved through pH
regulations. Thus, for example, it is generally possible to determine trivalent cations without
interference from divalent species by performing the titration in a medium having a pH of about
1. Under these circumstances the less stable divalent complexes do not form while the trivalent
ions are quantitatively complexed. Similarly, cadmium, which forms more stable EDTA complex
than magnesium can be determined in the presence of the latter ion by buffering the mixture to
pH 7 before titration. Eriochrome black T serves as an indicator for the cadmium end point
without interference from magnesium because the magnesium –indicator chelate is not formed at
this pH. Finally, inference from a particular cation can sometimes be eliminated through addition
of a suitable masking agent. This is simply an auxiliary ligand that preferentially forms highly
stable complexes with the potential interference and thereby prevents involvement of that ion in
equilibrium associated with either the titrant or the indicator. The cyanide ion, along or in
combination with other substances, finds wide use as a masking agent.
Titration curves for other poly-functional acids
Introduction
Titration of poly-functional acids can be derived using techniques similar to those employed in
the previous lecturers. To demonstrate how to calculate titration curves of poly-functional acids,
we will assume as a model system, a diprotic acid H 2A (K1 = 1.00 X 10-3, K2 – 1.00 x 10-7) with a
0.100 MH2A concentration. For the purposes of demonstrations, a 20.000 mL sample of 0.100 M
H2A will be titrated with 0.100M NaOH.
Objective
 Derive titration curves for other poly- functional acids
The titration will be divided into regions;
1- No NaOH added
2- NaOH added, but before the first equivalent point

3- At the first equivalent point
4- After the first equivalence point, but before the second equivalence point
5- At the second equivalence point
6- After the second equivalent point
No NaOH added
1- Treat the acid as a monoprotic acid “HA” with Ka = K1

2- ignore the other species present
NaOH added, but before first equivalence point
1- treat the calculations as a buffer consisting of H2A and HA

2- calculate from the amount of NaOH added, the molar concentration of H2A remaining and
the molar concentration of HA produced.
3- Substitute these concentrations into K1 to solve for [H3O-]
At the first equivalence point
1- At the first equivalence point, all of the H2 has been converted stoichiometrically to HA
2- The solution is identical to that obtained by dissolving NaHA in water and may be
calculated as such.
3- If NaHA is dissolved in water, the likelihood of HA gaining or losing a proton is roughly
equally likely (i.e H2A = [A2-]. This, at the equivalence point either equilibrium is likely.
HA1- + H2O H3O1+ + A2+
HA1- + H2O OH1+ + H2A
4- The first equilibrium is described by K 2. The second is describe by K1. The pH can be
calculated from K1 and K2 as follows;
K1K2 = [H3O1+] [HA1-] [H3O1+] [A2-]

[H2A] [HA1-]
K1K2 = [H3O1+] [HA1-] [H3O1+] [A2-]

[H2A] [HA1-]
K1K2 = [H3O1+] [H3O1+] [A2-]
[H3O1+] = √ K 1 K 2
Or, pH = pK1 + pK2
2
a. Note that the pH is simply the average of the two pK values, assuming equal portioning.
b. If we make no assumptions about equal partitioning, the pH can still be calculated as
follows;
Mass balance
CNaHA = [HA-] + [H2A] + [A2-]
Charge balance
[Na+]+[H3O+] = [HA-] + 2[A2-] + [OH-]
CNaHA + [H3O+] = [HA-] + 2[A2-] + [OH-]
Subtracting the charge balance from the mass balance

[H3O+] = [A2-] + [OH-] – [H2A]
Substituting to make all variable in terms of [HA]

[H3O+] = [A2-] + [OH-] – [H2A]
[H3O1+] = K2[HA1-] + Kw [H3O1+] [HA1-]

[H3O1+ [H3O1+] K1
Rearrangement and solving for [H3O+]
[H3O1+] = √ K1K ¿ ¿ ¿
2
(To solve for [H3O+] , it is generally assumed that CNaHA = [HA-]
After the first equivalence point, but before the second equivalence point
1- HA is being titrated with OH and a buffered solution of HA and A2- is being generated.
2- The equilibrium between HA- and A2- and is defined by K2

3- Calculate the [H3O+] calculate the [HA-] and [A2-] from the volume of NaOH added
beyond the first equivalence point and the total amount of acid initially present.
4- Substitute the concentrations into the K2 expression and solve for [H3O-]
At the second equivalence point

1- All the acid is in the A2- form
2- The solution is identical to a solution obtained by dissolving Na 2A in water and the[H3O-]
is calculated by the base hydrolysis of A2-.
A2-+ H2O OH1- + HA1-

Kt = Kw = [OH1-] [HA1-]
K2 [A2-]
3. The concentration of [OH-] and [HA-] are assumed to be equal. [A2-] is assumed to be equal
to the original moles of divided by the total volume and [OH-] is solved for.
4. Assumption must be checked
After the second equivalence point

1- All the acid is converted to A2- and no buffer action is expressed due to the excess base.
2- The pH of the solution is controlled by the excess NaOH added beyond the second
equivalence point
3- [OH-] is calculated from the excess NaOH beyond the second equivalence point and [H 3O-]
is calculated from the [OH-].
Titration curves for argentometric methods

Plots of titration curves are normally sigmoidal curves consisting of pAg (or P Analyte) versus
volume of AgNO3 solution added.
In the example below, chloride is titrated with silver
Low [Ag1+] Low [CI1-]

pAg Ag1+ + C11- AgC1
(or pCI]
High (CI1-] High (Ag1+]
mL Ag NO3 solution
The points on the curve can be calculated given the analyte concentration AgNO3 concentration
and the appropriate Ksp
The titration curve is normally broken down in three regions for the purposes of calculations and
a function for pAg is determined for each region.
1- Pre- equivalence region
2- Equivalence point
3- Post- equivalence region
Model titration: 50:00mL of 0.0005M NaBr titrated with 0.010 M AgNO3
Relevant equilibrium and constants:
1. Ksp = 5.2x 10-13 = [Ag+][Br-]
2. Charge balance: Na+] + [Ag+] = [Br-] + NO3-]
3. Note that we are ignoring hydronium and hydroxide ion contributions from the water.
Pre- equivalence: assume for the sake of calculations that 5:00mL of 0.010 MAgNO 3 has been
added to the 50.00mL aliquot of 0.0005M NaBr. (All volumes up to equivalence would be
calculated the same way).
1. Silver ion will combine with the bromide ion
Ag+ (aq) + Br-(aq) -------- AgBr(s)
2. Once formed, the solid AgBr may “back –dissolve,” producing trace amounts of silver ion.
It is this “back-dissolved” [Ag] that must be calculated to obtain pAg.
3. At equilibrium
[Br-] equilib, total = [Br-] unreacted + [Br-] back-dissolved
4. The back-dissolved [Br-] back-dissolved is assumed to be negligible. Thus,
[Br-]equilib, total = [Br-] unreacted
Br-] unreacted = ≠ total moles NaBr initially – ≠moles AgNO3 added
Total volume of combined solutions
= {50.00mL} {0.00500M}- {5.00m}{0.0100M}

5.00mL + 5.00mL
= 3.64 x 10-3MBr1-
5. Once the bromide concentration is determined, the silver ion and pAg concentration are
calculated using Ksp:
Ksp = [Ag1+] [Br1-]
Rearranging
[Ag1+] = Ksp
[Br1-]
K sp
-log Ag1+] = -log ⌈ 1−¿
Br ⌉¿
−13
5.2 x 1 0
pAg = - log ⌊ −3
⌋ = 9.84
3.64 x 10
6. Also, the assumption made [Br-] from back- dissolved AgBr is much less than the unreacted
[Br-] must be checked:
pAg = 9.84
[Ag+] = 10-9.84 = 1.4 x 10-10 M= [Br-]back-dissolved.
[Br-]back-dissolved = 1.4 x 10-10 M<<< 3.64 x 10-3 M = [Br-]unreacted
At the equivalence point: [Ag+] =[Br-]
Complex formation and precipitation titrations

Introduction
Complex formation titration are used to titrate cation via complex formation reagents. Most if
not all, metals form coordination complexes with anions or molecules. For example;
Fe2+ + 6CN Fe (CN)64
Molecules/anions that react with metal ions must donate an unshared pair of electrons to form a
coordinate covalent bond.
Objectives

 Define most of the terms related to complex formation
 Discus the titration methods based upon utilizing silver nitrate as a precipitating agent
 Derive titration curves for argentometric methods
 Discuss the use of adsorption indicators in argentometric titrations
Terminology
The metal ion (or cation) in a complex is called the central atom
The electron- pair donating species is called the ligand
The number of bonds the central atom can form is called its coordination number
Key points in complex formation

The complex can form only when;
1- The central atom accepts an electron pair from one or more ligands
2- The ligand possesses at least one electron pair to donate
3- The bonding (coordinate covalent bonding) occurs
A number of common anionic and molecular ligands can form complexes
1- Anionic ligands include halides, SCN, CN, OH, RCOO-, S2-, C2O42- (oxalate), etc.
2- Molecular ligands include water, ammonia, RNH2 (amines) C5H5N (pyridine)
H2NCH2CH2NH2 (ethylenediamine) etc.
Ligands that have (or share) only one electron pair are called unidentate
1- “Dentate” = at tooth –like projection
2- For example, ammonia is unidentate
Cu2+ + 4NH3 Cu(NH3)42+
Bidentate ligands share two electrons, pair. Examples would include;
1- Glycine complexed with cooper (II)
2- Ethylenediamine complexed with zinc ion
Multidentate ligands complexed to metal ions are called chelates always have a “chelate ring”
for example, the zinc -8 –hydroxyquinolate complex.

As titration for measuring metal ions, multidentate ligands are preferred.
1- They generally react more completely (have larger Kf values), giving sharper
endpoints/equivalence points.
2- They generally react in a single step (all or none) processes, (i.e. no intermediate species
must be considered)
Precipitation titrimetry – formation of insoluble metal –ligand precipitates
We will focus only on argentometric methods- titration methods based upon utilizing silver
nitrate as a precipitating agent.
“argentums” is Latin for “silver”
Silver ion is extremely useful in precipitation reactions including;
1- Halides (AgC1, AgI)

2- Divalent anions (Ag2CO3)
3- Merceptans (Ag2S)
4- Fatty acids
1- Since silver and bromide have been reacted at the stoichiometric ratio, both the silver and
bromide ion remaining in solution comes from back dissolving of the AgBr precipitate
2- Ksp can be used to calculate pAg
Ksp = [Ag+] [Br-] = [Ag+]2
[Ag+] = √ K sp = √ 5.2 x 1013 = 7.21 x 10-7
pAg = -log (7.21 x10-7) = 6.14
Region beyond the equivalence point [Ag+] > [Br-]
1- Excess silver ion has been added and thus, the back- dissolving of AgBr is negligible.
2- The excess silver ion is calculated from the volumes reacted. Assume for the sake of
example that 27.00ml of 0.10M AgNO3 has been added to the 50.00mL aliquot of
0.005M NaBr:
Csiverion = ≠total moles AgNO3 added - ≠totalmoles NaBr initial
total ≠mL of solution
= (27.00m)(0.0100M) – (50.00mL)(0.00500M)

50,00mL + 27.00mL
= 2.6 x 10-4 MAg1+
pAg = -log (2.6 x 10-4MAg1+) = 3.59

Observation about argentometric titrations
High reagent concentration give sharper, more dramatic equivalence point changes in pAg and
better endpoints.
The smaller the Ksp, the more complete the precipitation reaction and the sharper the equivalence
region changes. An approximately two pAg change around the equivalence point is needed for
the titration to work.
Both Ksp and the reagent concentration affect the choice and use of an endpoint indicator.
Endpoint indicators for argentometric titrations

Like acid –base indicators, indicators for argentometric titrations selected to produce a colour
change at or near the equivalence point. Normally the indicator is selected to react with the
added titrating agent, not the analyte. If A is the analyte, R the titrating agent and in is the
indicator.
A+ R AR (s)
In (colour) + R InR (new colour)
1. Note that to make the indicator change colour, excess R must be added. Obviously, the
smaller the excess added to cause the colour change, the smaller the end point error.
2. This means that the indicator should give large colour changes at very low concentrations
Desires properties of indicators for argentometric titrations
1- Low InR concentrations are needed to produce dramatic colour changes
2- The indicators should not significantly disturb the equilibrium between the analyte and
the titrating agent.
3- The concentration of the reagent should be adjusted such that the transition range of the
indicator is complete spanned by the change in pAg in the equivalence regions.
The indicators are commonly employed in the following titration procedures
Mohr’s methods for determining the halide ion concentration

The Mohr method was first published in 1855. This procedure is now widely applied to the
titration of chloride ion and bromide ion with standards silver nitrate. Chromate ion is used as the

indicator, the end point being signaled by the appearance of a brick-red silver chromate Ag 2 CrO4
precipitate.
Calculation from its solubility –product constant (1.1 x 10-12) reveals that the molar solubility of
silver chromate is several times greater than silver chloride. Thus, the latter precipitate tends to
form first in the titration mixture. By adjusting the chromate concentration to a suitable level,
formation of the silver chromate can be retarded until the silver ion concentration in the mixtures
rises to the level corresponding to the theoretical equivalence point. Generally, a chromate
concentration of 6 x 10-3 M imparts such an intense yellow color to the solution that formation of
silver chromate is not easily seen. As a result, an indicator concentration smaller than 5x 10 -3 M
must be employed.
Attention must be paid to the pH of the medium because the equilibrium
2CrO42- + 2H+ = Cr2O72- + H2O is disciplined to the right as the hydrogen ion concentration is
increased; since silver dichromate is considerately more soluble than the chromate, the indicator
reactions in acid solution required far higher silver ion concentrations, if indeed it occurs at all. If
the medium, is made strongly alkaline there is danger that silver will precipitate as its oxide.
2Ag+ + 2OH- = 2AgOH = Ag2O + H2O
Thus, the determination of chloride by the Mohr method must be carried out in a medium that is
neutral or nearly so (pH7 or 10). The presence of either solid, bicarbonate or of borax in the
solution tends to maintain the hydrogen ion concentration within suitable limits.
Volhard method
This method involves titration of silver ion with iron (III)/ thiocyanate (SCN -) indicator. It was
first published in 1874 and the reactions involved are;
Thus
Ag+ (aq) + SCN- (aq) = AgSCN (s)
Iron (III) ion serves as the indicator; imparting a red coloration to the solution with the first slight
excess of thiocyanate:
Fe3+ + SCN- = Fe (SCN)2+

red
The titration must be carried out in acid solution to prevent hydrolysis of the iron (III). The
titration error in the Volhard method is small because the indicator is highly sensitive to
thiocyanate ions. Thus, 1 or 2 ml of a saturated ion (III) ammonia sulfate solution (about
40percent) will impart a faint orange colour to 100ml of solution that also contains about 0.1 ml
of 0.001 of thiocyanate. In order to avoid a premature end point in the titration, however, the
solution must be shaken vigorously and the titration continued until the indicator colour is
permanent. This precaution is necessitated by the strong tendency of silver thiocyanate to absorb
silver ions from the solution, thus, inhibiting the rate at which they combine with the thiocyanate.
The most important application of the Volhard method is for the indirect determination of halide
ions. A measured excess of standards silver nitrate solution is added to the sample, and the
excess silver ions are determined by back titration with a standard thiocyanate solution. The
requirement of strongly acid environment represents a distinct advantage for the Volhard
technique over other methods for halide analysis because such ions as carbonate, oxalate, and
arsenate (which form slightly soluble silver salts in neutral media) do not interfere at high
hydrogen ion concentrations.
In contrast to the other silver halides, silver chloride is more soluble than silver thiocyanate. As a
consequence, the reaction.
AgCI (s) + SCN (aq) = AgSCN (s) + CI (aq)
Occurs to a significant extent near the end point in the back- titration of excess silver ion. The
result is an end point that fades and an over consumption of thiocyanate ion, which in turn leads
to low values for the chloride analysis.
A number of schemes have been developed to overcome this source of error. Filtration followed,
by titration of an aliquot of the filtrate, yields, excellent results, provided the precipitated silver
chloride is first briefly digested; the time required for filtration is, of course, a disadvantage.
Probably the most widely employed modifications is that which consists of coating the silver
chloride precipitate with nitrobenzene, thereby substantially removing it from contact with the

solution. The coating is accomplished by shaking the titration mixture with a few milliliters of
the organic liquid prior to back- titration.
It has been shown that these techniques are quite unnecessary, provided a sufficiently high
concentration of ion (III) ion is employed.
The Volhard method may be applied to the analysis of any anion that forms a slightly soluble salt
with silver nitrate. Steps must be taken to prevent interference from precipitate that are most
soluble than silver thiocyanate.
Adsorption indicators
Adsorption indicators are organic compounds that tend to be adsorbed onto the surface of the
solid precipitate in a precipitation titration. Under proper circumstances, the adsorption (or the
reverse desorption process) can be made to occur at or near the equivalence point in the titration
thus, the appearance or disappearance of a colour on the precipitate signals the end point.
Titration based on adsorption indicators are sometimes called Fajans methods.
An example of an adsorption indicator is the organic dye fluorescent, which is employed as an

indicator for the titration of chloride ion with silver nitrate. In aqueous solution this compound
partially dissociate into hydrogen ions and negatively charged fluoresceinate ion forms a highly
colored silver salt of limited solubility in its application as an indicator, however, the
concentration of the dye is never large enough to exceed the solubility product for silver
fluoresceinate.
In the early stages of a titration of chloride with silver ions, the dye anion is not appreciably
adsorbed by the precipitate. It is, in fact, repelled from the surface by the negative charge,
resulting from absorbed chloride ions. When the equivalence point is passed, however, the
precipitate particles become positively charged by virtue of the strong adsorption of excess silver
ions and under these conditions, retention of fluorescienate ions in the counter-ion layer occurs.
The net result is the appearance of the red of colour of silver fluoresceinate on the surface of the
precipitate. This is an adsorption (not a precipitation) process. Fluorescienate was used in the
Fagan’s analysis originally, but the dichloro derivative is more commonly used now.

Requirement of dye and precipitate upon which successful indicators action depends;
1- Since this is a surface effect, the precipitate should be produced in a highly dispersed
state, here is one of the few instances where the analytical chemist is interested in
producing and preserving a colloid.
2- The precipitate must strongly adsorb its own ions. Most precipitates meet this
requirement.
3- The dye must be strongly held by the primarily adsorbed ion
Titrations involving adsorption indicators are rapid, accurate and reliable. At the same time,
however, their application is limited to a relatively small number of precipitation reactions in
which a colloidal precipitate is rapidly formed. Furthermore, care must be taken to control the
acidity of the solution in which they are used. In the presence of high electrolyte concentrations,
end points with these indicators tend to be less satisfactory, owing to coagulation of the
precipitate and the consequent reduction of surface on which adsorption can occur. Finally, some
adsorption indicators sensitize precipitates containing silver ion towards photodecomposition;
this reaction may also lead to errors.
Acid –base titration in non-aqueous media
Introduction
For a volumetric method to be meaningful, the reaction between the species being titrated must
be relatively complete. We have seen earlier that completeness of reaction is directly related to
the dissociation constants of the participants in a neutralization system.
Many acids and bases that are too weak (Ka <10-8) for determination in an aqueous medium can
be successfully titrated by using solvents, other than water, the emphasise such acidic or basic
character as the solutes may possess.
Objectives
 Discuss the role of acid –base titration in non-aqueous media
 Discuss the effect of dielectric constant on behavior of solutes
 Discuss how solvent can be chosen for such titrations
 State the application of non- aqueous titrations

We have previously done some classification of solvents. For purpose of clarify, we can define
them again though in a slightly different manner.
Amphiprotic solvents: These possess both acidic and basic properties and are capable of
undergoing self- dissociation or auto photolysis. Although water is the most common
amphiprotic solvent, many other substances exhibit analogous behavior
Thus
2H2O = H3O+ OH
2C2H5OH = C2H5OH2+ + C2H5O-
2HOAC = NH4+ + NH2
Or in general
2SH = SH2+ + S.
Where SH represents the amphiprotic solvent molecule and SH 2+ the solvated proton, the base
the corresponds to the anion S-. In contrast to water and the alcohols, some amphiprotic solvent
such as acetic acid, sulfuric acid, or formic acid have considerably stronger acidic than basic
properties; others such as ammonia or ethylenediamine, have stronger basic than acidic
tendencies.
Aprotic or inert solvents: These exhibit no appreciable acidic or basic properties and do not
undergo autoprotolysis to any detectable extent. Examples include; benzene, carbon tetrachloride
and pentane.
Finally, there exist a number of solvents with basic properties but essentially no acidic
tendencies. These include ketones, ethers, esters, and pyridine. Such solvents do not undergo
autoprotolysis.
As we have noted, a satisfactory end point to a titration requires that chemical reactions involved
to be nearly complete. Alternation of the solvent often exerts a profound effect on the
completeness of a neutralization reaction. If proper choice of medium is done, acids or based that
are too weak in water for titrations can be satisfactory determined. In this section we are
concerned with the effects of amphiprotic solvent on the extent to which an acid-base reaction
proceeds towards completion.

The completeness of neutralization reactions
In water the titration of a weak base B with a standard strong acid can be formulated as;
B+H3O+ = BH+ +H2O
And we can use the magnitude of the equilibrium constant for this reaction as a measure of its
completeness that is;
Kequil = [BH+]
[B][H3O+]
This is ideally equal to Kb/Kw
Effect of dielectric constant on behavior of solutes
Thus far we have shown that the strength of a solute as an acid or base is determined in some
measure by the acidic or basic character of the solvent. To complete this discussion, we must
now consider the dielectric behavior of the solvent, which also influences the strengths of solute
acids or bases.
The dielectric constant of a solvent measures its capacity for separating oppositely charged
particles. In a solvent with a high dielectric constant such as water (DH 2O= 78.5) a minimum of
work is required to separate a positively charged ion from a negatively charged one; for a solvent
with a low dielectric constant such as acetic acid (D HOAC=6), a greater amount of energy is
required to accomplish the process. Methanol and ethanol have dielectric constant of 33 and 24
respectively and are intermediate in their behavior.
The dielectric constant of the solvent plays an important role in determining the strengths of
soluble acids or based in so for as the ionization process produces oppositely charged species.
For example, when an uncharged weak acid HA is dissolved in an amphiprotic solvent SH, the
dissociation process requires the separations of the charged particles SH2+ and A:
HA + SH = SH2+ +A-
The same would be true upon solution of an uncharged base B:
B+ SH = BH+ +S-
Processes of this sort would be expected to proceed further to the right in a solvent such as water
than they would in methanol or ethanol because less work has to be expended in the dissociation
process. The magnitude of this effect can be large, for example, the dissociation constant for

acetic acid in water in approximately 10-5, whereas in ethanol it is somewhat smaller than 10-10.
Other acids of this type show similar decreases.
The strength of an acid or base is not affected significantly by the dielectric constant of the
medium when the dissociation reaction does not involve a charge separation. For example, the
following equilibrium would not be altered by changed in dielectric constant of the solvent SH.
BH+ + SH = SH2+ + B
A-+SH = HA +S
It should be emphasized the solutes which are strong electrolytes in water may no longer be
completely dissociated in solvents with very low dielectric constants. For such media other
relationships must be sought.
Choice of amphiprotic solvents for neutralization titrations
We have indicated that the completeness of a neutralization reaction is directly depended upon
the ionization constant of the solute acid or base and inversely related to the autoprotolysis
constant of the solvent. Furthermore, we have shown that the first of these factors, the ionization
constant, is dependent upon the acidic or basic properties and the dielectric constant of the
solvent. Thus, the best choice of solvent for a given titrations hinges upon three interrelated
properties.
1- Its autoprotolysis constant, a solvent with a low constant being desirable

2- Its properties as a proton donor or acceptor. For the titration of a weak base; a solvent
with strong donor tendencies is better (that is and acidic solvent) and for the analysis of a
weak acid, a solvent that is a good proton acceptor is desirable.
3- Its dielectric constant, the higher the value the better.
In addition, of course, the solvent must be one in which the sample is reasonably soluble.
Glacial acetic acid is often chosen as solvent for the titration of very weak based because of its
tendency to donate protons and thus enhance the strengths of dissolved bases. Its autoprotolysis
constant (3.5 x10-5) is also somewhat favourable than that for water. On the other hand, its low
dielectric constant (D=6) partially offsets these effects. In turns out that the two advantageous

properties outweigh the single disadvantage, however, and acid is generally superior as a solvent
for the weak bases. It will be clearly inferior to water for titration of weak acids because of its
weakness as a proton acceptor. It is profitable to consider formic acid in the role of an acidic
solvent. Like acetic acid, it is a much better proton donor that water, furthermore, in contrast to
acetic acid, formic acid has a high dielectric constant (D=62), comparable with water. On these
two counts then it would appear to be an ideal solvent for the titration of weak based
unfortunately, however, is autoprotolysis constant is much large than that of water and acetic
acid, having a value of about 8 x10 -7. As a consequence, formic acid appears to offer little
advantage compared to water despite its two very desirable properties.
Methanol and ethanol have been widely applied as solvent media for acid –base titrations. It is of
interest to examine their properties in the light of the foregoing discussion. Both substances are
classified as neutral because their proton donor and acceptor properties do not differ markedly
from water. Both have very advantageous autoprotolysis constants compared with that of water
(2x10-7) for methanol and 3x10-20 for ethanol). On the other hand, the dielectric constants for the
two solvent are respectively 33 and 254 as compared with 78.5 for water. Their smaller dielectric
constants offset the advantage of their lower, autoprotolysis constant in many applications. For
example, in ethanol, the ionization constants of most uncharged acids such as benzoic acid are
about 10-6 as great as in water, as the same time the ration of autoprotolysis constants in smaller
by nearly the same factor (3 x 10-6). Thus, the ration Ka/Kauto is only slightly more favourable
in ethanol than in water and the improvement in end points gained by use of this solvent is
modest. On the other hand, significant gin in realized by the use of ethanol for the titration of a
charged weak acid such as the ammonium ion. Here, no charge separation is involved in the
dissociations process.
NH4+ + C2H5OH = NH3+ C2H5OH2+
In contrast to be acid, then the dissociations of the acid NH 4+ is not significantly decreased in
ethanol. The reaction of NH4+ with a strong base is, however, much more complete in ethanol
because of the low autoprotolysis constant of the solvent. As a consequence, NH 4+ can be titrated
satisfactorily in ethanol but not in water.
End point detection in a non-aqueous titration.

Many acid –base indicator used for aqueous titrations are also applicable in non-aqueous
solvents. Unfortunately, however, their behavior in an aqueous environment cannot be
extrapolated to predict their properties in ion aqueous solutions. The limited information
available with respect to these properties in solvents other than water makes the choice of
indictors largely a matter of experience and empirical observation. The most popular method of
end –point detection for non-aqueous titration involves the measurement of the potential of an
electrode system that is sensitive to the concentration of the solvated proton in the solvent.
Application of non- aqueous titration

The titrations are commonly employed in the following ways;
 Analysis of amines
 Analysis of amino acids
Introduction to analytical separations

Chromatography
Chromatography encompasses as diverse group of separation methods that are of great
importance to the analytical chemist. The method is often useful in separation, isolation, and
identification of the components of mixtures that might otherwise be resolved with difficulty.
Objectives
 Define chromatography
 Discuss the different chromatographic techniques
 Draw and label a gas chromatograph
 Define most of the terms related to chromatography
 Discus the uses of chromatography
1- “Chroma” is Greek for “colour”
2- “Graphein” is Greek for “to write”

Originally, chromatography was used to separate plant pigments. “Colors” developed and
separated as plant homogenates were passed through calcium carbonates –packed columns.
Common features of chromatographic methods include;

 A stationary phase, often packed into a column through which the sample is passed to
effect separation. Stationary phases can be almost anything.
 A mobile phase, the liquid (or gas) that carries the sample/analyte through the
stationary phase
Because different analytes have different binding affinities for the stationary phase, their
movement through the stationary phase will be retarded varying degrees, affecting separation.
Classification of chromatographic methods

Adsorption chromatography
Historically, the first chromatographic techniques were based on adsorption. It was discovered
by a Russian botanist M, Tswett, who in 1903, employed the technique to separate the various
colored components of a plant extract. A quarter of a century was to pass before the significance
of his discovery was fully appreciated by investigators engaged in the separation of biological
and organic materials.
In all early applications, the procedure was limited to the separation of colored substances (thus
the name chromatography) that could be identified by their appearance. A glass column was
packed with a finely divided adsorbents such as silica, alumina, calcium, carbonate, or sucrose,
the adsorbent was then wetted with a solvent and a solution of the sample was introduced at the
top of the column. The column was developed by washing with further portions of the solvent
until coloured bands of the solute appeared at various positions along its length. The various
colored fractions were recovered by pushing the packing out of the column, cutting it into
sections, and testing each with a solvent that would cause the component to be desorbed.
The method was later simplified by washing the column with sufficient solvent until each of the
adsorbed components has been eluted in turn and collected. Still later, methods, making use of
such properties as refractive index and ultraviolet absorbance were employed, to indicate when
components of the mixture have been washed from the columns this broadened the scope of the
procedure to include colourless materials.

Liquid –liquid partition chromatography
In partition chromatography a column is packed with a finely divided solid absorbent that serves
as a support for a stationary liquid phase. For example, a thing film of water adsorbed on silica
gel is often employed. The mixture to be separated is added at one end of the column and then
eluted with a solvent that is immiscible with the water held on the gel. The rate of movement of
the individual solutes through the columns depends upon their partition coefficient between the
mobile non- aqueous phase and the stationary aqueous phase.
Application of partition chromatography

The method finds extensive use in separations of various amino acids and acetulated amino acids
from proteins. Other applications of the techniques have included separation of closely related
fatty acids, aromatic acids, and a variety of other organic mixtures.
Column chromatography
1- The stationary phase is packed into a glass column, tube or other cylinder container
2- Mobile phase and analyte are passed through the column under pressure or by gravity
consider the liquid chromatography example shown below
3-
Ion exchange chromatography

While most other types of chromatography are used principally for separations of complex
organic substances, ion exchange chromatography is particularly well suited for the separation

based on exchange of ions in the stationary phase. It has also proved to be extremely useful for
the separation of amino acids.
The stationary phase in ion exchange chromatograph consists of beads made of a polystyrene,
polymer cross- linked with divinylbenzene. The cross-linked polymer (resin) has free phenyl
groups attached to the chain, which can easily be treated to add ionic functional groups. There
are basically four types of ion exchange resins used in analytical chemistry and these are
summarised in table ****
Cation exchange resins

These resins contain acidic functional groups added to the aromatic ring of the resin. The strong-
acid cation exchangers have sulfonic acid groups. –SO3H, which are strong acids much like
sulfuric acid. The weak –acid cation exchangers have carboxylic acid groups, CO2H, which are
only partially ionized. The protons on these groups can exchange with other cations:
nRzSO3H+ + Mn+ = (RzSO3)n M+nH+
nRzCO2H+ + Mn+ = (RzSO2)n M+nH+
where Rz represents the resin. The equilibrium can be shifted to the left or right by increasing
[H+] or [Mn+] or decreasing one with respect to the amount of resin present.
Types of ion exchange resins

Types of exchanger Functional exchanger Trade name
groups
Cation strong acid Sulfonic acid Dowexa 50: amberliteb IRI
120; Ionacc CGC-240
Rexynd 101: Permitite Q
Weak acid Carboxylic acid Amberlite 50; Ionac CG270;
Rexyn 102: Permitit H-70
Anion strong base Quaternary ammonium ion Dowex 1; Amberlite IRA
400; Ionac AGA-542; Rexyn
201; Permutit S-1
Weak base Amine group Dowex 3; amberlite IR 45;
ionac AGA-316; Rexyn 203;
permit W

Cation exchange resins are usually supplied in the hydrogen ion form, but they can easily be
converted to the sodium ion form by treating with a sodium salt. The sodium ions then undergon
exchange with other cations. The exchange capacity of a resign is the total number of equivalents
of replaceable hydrogen per unit volume or per unit weight of resign and it is determined by the
number and strength of fixed ionic group on the resin. The ion exchange capacity affects solute
retentions and exchangers of high capacity are most often used for separating complex mixtures,
where increased retention improves resolution.
Weak acid- cation exchange resigns are most restricted in the pH range in which they can be
used, from 5 to 14. While the strong- acid resins can be used from pH 1 to 14. At low pH values,
the weak acid- exchangers will “hold on” to the protons too strongly for exchange to occur. Also,
the weak acid- cation exchangers will not completely remove the cations of every weak bases,
while strong –acid resins will. This is analogous to the incompleteness of a weak acid- weak
base reaction. Weak acid resins are generally used for separating strongly basic or
multifunctional ionic substances such as proteins or peptides that are often firmly retained by
strong-acid ion exchangers while strong acid resins are more generally preferred especially for
complex mixtures.
Anion exchange resins

These are resins in which basic groups on the resin can be exchanged with other anions. There
are strong base groups, (quaternary ammonium groups) and weak –base groups, (amine groups).
The exchange reactions can be represented by;
nRzNR3H+ + An- = (RzNR3)nA+ nOH+
and
nRzNR3 +OH + An- = (RzNR3)nA+ nOH+
where R represents organic groups, usually methyl
The strong base exchangers can be used over the pH range 0 to 12, but the weak –base
exchangers only over the range of 0 to 9. The latter exchangers will not remove very weak acids,
but they are preferred for strong acids may be retained by strong-base resins, such as sulfonates.
Cross –linkage

The greater the cross – linkages of the resin, the greater the differences in selectivities.
Generally, cross –linkage also increased the rigidity of the resin, reduces swelling, reduces
porosity and reduces the solubility of the resin. In general, medium –porosity materials are used
for low – molecular –weight ionic species and high porosity materials are used for high
molecular weight ionic species. The degree of cross-linkages is expressed by the manufacturers
as percent of divinylbenzene. Generally, cross- linkage of 8 to 10% is used.
Some applications of ion exchange chromatography
 Purification. One of the most important applications of ion exchange is the deionization
of water, which, although non-analytical, offers great advantage for the analytical
chemist. The water is passed through a mixed –bed ion exchange resin (commercially
available) that contains both a strong –acid cation and a strong –base anion exchange
resin, when water containing a salt, such as CaCI 2 is passed through the column, the
Ca2+ ion is exchanged for two H+ ions and the two CI- ions are for two OH- ions. The net
result is that the salt is exchanged for H2O. Organic constituents, however, are not
removed and sometimes the water is passed through a column of activated charcoal for
removal of organic matter.
 Concentration of trace material. Ionic materials that exist at very low concentrations
can often be concentrated by collecting them on an ion exchange column and then eluting
theme with a much smaller volume of an appropriate eluting agent. In this manner, the
ions are also often removed from the bulk matrix so they may be obtained in purer form.
Ion exchange is commonly employed in the concentration of trace elements in seawater.
 Analytical separation. The most important application of ion exchange chromatography
is seen in analytical separations for example, separations of metal ions and amino acids.
Halide ions and alkali metals can also be separated using the method.
Planar chromatography
1- The stationary phase is supported by a flat surface (e.g. a glass plate, a plastic sheet,
paper etc.)
2- The mobile phase and analyte pass through the stationary phase by capillary action and/or
gravity

Paper and thin layer chromatography
Both methods are simple and require minimal sample size and both find wide use in
biochemistry and organic chemistry.
Paper chromatography
In this technique, a solution of sample is placed near one end of a strip of heavy filter, paper. The
paper is then suspended vertically, with the lower edge (containing the sample) immersed in a
developing solvent. Capillary action causes the solvent to move up the paper, each component of
the sample is carried along at an individual rate. To aid in identification, the paper may be
sprayed after development with a reagent that forms colored products with the components. The
paper may be cut into pieces for recovery of the components, or the analysis may be completed
by measuring the size of the coloured spots.
Thin- layer – chromatography

This technique is operationally similar to paper chromatography. Instead of a piece of paper, a
thin layer of a finely divided slid in supported on a plane surface. A thin- layer, plate can be
prepared by spreading an aqueous paste (slurry) of the finely ground adsorbent over the surface
of a glass plate or a microscope slide. The slide is then allowed to stand until the layer has set up.
In some cases, it may be heated in an oven for several hours. Adsorbent materials used for thin-
layers chromatography include silica gel, alumina and powdered cellulose.
Solvent front (moving

up in plate)
Samples
Fudicial line (where
sample are applied
Description of column elution chromatography

Terminology;
1- Eluent- mobile phase, solution fed into the top of a column to elute a sample.
2- Eluate- species eluted from the bottom of a chromatographic column

3- Chromatogram- a plot of the detector signal (or any other function of analyte
concentration) verses elution time (or elution volume)
4- Chromatography –device (instrument) that performs the chromatographic separations
(e.g. the HPLC instrument).
5- Absolute retention time- time (from the moment of injection) required for a sample to
reach the detector (or be eluted from a column)
6- Relative retention time – time relative to some internal standard required for a sample to
be detected (or elute from a column)
7- Dead time – Time between injection of a sample and the appearance of the first peak on
the chromatogram. (Air is often injected on purpose as in internal reference).
The column is packed with a solid phase and equilibrated by passing the mobile phase through
the column. An aliquot of mobile phase containing dissolved analytes is applied to the top of the
column and allowed to “drain” into the bed of the column. Mobile phase is continuously fed into
the top of the column to flush the analytes through. As the analytes pass through the column,
they “partition” between the mobile phase and stationary phase.
 Analytes with lower affinity for the stationary phase spend less time bound to the
column and pass through quickly.
 Analytes with higher affinity for the stationary phase spend more time bound to the
column and pass through more slowly.
Detector placed at the bottom of the column may be used to sense the passing of analytes.
 The detector may measure u.v/visible light absorbance, refractive index, fluorescence,
conductivity etc. changes related to the passing of analytes out the column.
 The output from the detector is used to plot a chromatogram; a plot of detector output
versus time (or volume eluted)

Analysis of chromatograms
Retention times of peaks may be useful for qualitative identification of specific species in
mixtures.
 Under a given set of conditions, a single analyte will always have the same retention
time
 A control sample of the analyte is run to determine the retention time of the analyte, and
the presence of the analyte in a complex, unknown sample us usually determined by the
presence of a peak identical in retention time to the control sample.
 It is always best to repeat the analysis with a different set of chromatographic conditions.
If the control sample and complex, unknown sample have peaks that match under more
than one set of chromatographic conditions. It is usually safe to assume the they are the
same species.
Peak heights and areas may be used to derive quantitative data from chromatograms
 The concentration of an analyte is proportional to the area (or height) of the peak
observed on the chromatogram.
 To quantity an analyte a series of control runs with varying amount of standard
analyte must be run to prepare a standard curve (a plot of peak area versus amount of
standard run).
 The unknown sample is then run under conditions identical to the control runs, and
the areas (or height) of the analyte peak is determined. Area is usually determined by;
a. Electronic integration of the peak
b. Approximation by “triangulation
Area = ½ [ Base] [ Height]

c. Cutting out the peak with scissors from a paper of the chromatogram and weighing
the paper peak. The weight is proportional to area.
The figure below is a schematic diagram of a gas chromatograph
The sample is rapidly injected by means of a hypodermic syringe through a rubber septum into
the column. The sample injection port, column and detector are heated to temperature at which
the sample has a vapour pressure of at least 10 torr. The injection port and detector are usually
kept somewhat warmer than the column to promote rapid vaporization of the injected sample and
prevent sample condensation in the detector. Liquid samples of 0.1 to 10µL are injected, while
gas samples of 1 to 10mL are injected. Gases may be injected by means of a gas-tight syringe or
through a special gas inlet chamber or constant volume (gas sampling value)
Separation occurs as the vapour constituents partition between the gas and the liquid phases in
the same manner as in the other chromatographic processes. The carrier gas is a chemically inert
gas available in pure form, such as argon, helium, nitrogen, or carbon dioxide. A high –density
gas gives best efficiently, but a low- density gas gives faster speed. The choice of gas is often
dictated by the type of detector.
The sample is automatically detected as it emerges from the column (at a constant flow rate),
using a variety of detectors whose response is dependent upon the composition of the vapour.
Usually, the detector contains a references side and a sampling side. The carrier gas is passed
though the references side before entering the column and emerges from the column through the
sampling side. The response of the sampling side relative to the reference side signal is fed to a
recorder where the chromatographic peaks are recorded as a function of time. By measuring the
retention time (the minutes between the time that sample is injected and the time the

chromatographic peak is recorded) and comparing this time with that of a standard of the pure
substance, it may be possible to identify the peak (agreement of retention times of two
compounds does not guarantee the compounds are identical). The area under the peak is
proportional to the concentration and so the amount of substance can be quantitatively
determined. A gas can move much more rapidly through a packed column that a liquid can and
so chromatographic separations require only minutes, as compared with much longer times for
other chromatographic techniques (an exception is high –performance liquid chromatography).
in addition, such the peaks are automatically recorded the entire analysis time is amazingly short.
This, coupled with the very small sample required explains the popularity of the technique. This
is not to exclude the more important reason that may of the analyses performed simply cannot be
done by other methods.
In a chromatographic run;
 Sample is injected through a rubber septum and is instantly vaporized
 The vaporized sample is carried through the column by a carrier gas (mobile phase)
 Components pass out the column, they pass through a detector system
Liquids used to coat column packings are selected based upon their polarity and ability to
interact with the analyte(s)
Generally,
a. Polar coatings blind polar solutes
b. Non-polar coating binds nonpolar solutes
Analytes of similar polarity elute in order of boiling points, lowest boiling points first
The boiling points are different enough, separation is achieved.
General application of gas chromatography

Gas chromatography is perhaps the most potent tool available for the resolution of mixtures of
organic compounds. It is therefore important in both qualitative and quantitative analysis.
 Gas chromatograms are widely used as criteria of purity for organic compounds.
Contaminants if presents are revealed by the appearance of additional peaks. The areas
under the peaks provide rough estimates of the extent of contamination. The technique is
also useful or evaluating the effectiveness of other purification procedures.

 Theoretically, retention –time data is useful for the identification of components of
mixtures. However, the number of variables that need to be controlled in order to yield
reproducible retention times limits the applicability of the technique.
 Gas chromatography provides an excellent means of confirming the presence of a
suspected compound in a mixture provided that a sample of the pure compound is
available. No new peaks in the chromatogram of the mixture should appear upon addition
of the pure compound and enhancement of one of the existing peaks should be observed.
Gas chromatography is often teamed with infrared or mass spectrometry to provide a powerful
tool for qualitative identification. In this application the products for the columns are collected in
a cold trap as they appear, and are subsequently identified by their spectra.
Specific applications of gas chromatography include;

 Analysis of ketones, aldehydes, aromatics, steroids, pesticides, blood compound, old
petroleum and petroleum products, foods and pharmaceuticals
 Air pollution
 Analysis of anything that can be volatilized and pushed through a column
END

INTRODUCTORY ANALYTICAL CHEMISTRY 1 - Final

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INTRODUCTORY ANALYTICAL CHEMISTRY 1 - Final

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MUNI UNIVERSITY

CHM 2201: INTRODUCTORY ANALYTICAL CHEMISTRY (3 CU)

WEEK CONTENT MODE OF DELIVERY

1 Introductory Lecture- Discussion, Lectures

Definition, application of Analytical Chemistry and the

Methods of representing concentrations.

3 Non-aqueous vis-à-vis aqueous titrations Discussion and Practicals.

4 Gravimetry – factors affecting solubility of precipitate: Discussion, Lectures,

 Ionic strength, pH and solvent

 UV-visible and IR spectrometry; principles and

Muhwezi Godfrey,Chem Department pg. 1

 Apparatus and applications.

7 Acid-base Titration Practicals.

Standardisation of hydrochloric acid, sodium hydroxide

12 Iodometric titrations Discussion, Practical

 Standardization of thiosulphate solution.

Muhwezi Godfrey,Chem Department pg. 2

13 Complexometric titrations Discussions, Practicals.

 Preliminary observation in complex formation

15  Indirect determination of sulphate. Practical

Suggested Reading List

Muhwezi Godfrey,Chem Department pg. 3

By the end of this lecture, you should be able to; -

 Define analytical chemistry

The scope/application of analytical chemistry

Muhwezi Godfrey,Chem Department pg. 4

Similarities between qualitative and quantitative analysis

Differences between qualitative and quantitative analysis

Muhwezi Godfrey,Chem Department pg. 5

The situation is as applicable to the chemistry of today as to that of the past.

 Every experimental investigation relies, to an extent, upon the results of analytical

Muhwezi Godfrey,Chem Department pg. 6

Classification of methods of quantitative analysis

Volumetric analysis. This involves the measurement of a volume

General classification Sub-classification Quantity measured

Muhwezi Godfrey,Chem Department pg. 7

Potentiometry Potential of an electrode in

Electro- analytical Conductimetry Conductance of a solution of

Coulometry Quantity of electricity

Polarography Current associated with

Muhwezi Godfrey,Chem Department pg. 8

The classification of methods as classical or instrumental is thus founded largely on

The Analytical process

By the end of the lecture, you should be able to;

Muhwezi Godfrey,Chem Department pg. 9

 Analyst’s skills and training in different techniques and instruments

An important consideration in selection is the accuracy required. Unfortunately, high reliability

A second consideration also related to economic factors, is the number of samples to be

2. Obtaining a representative sample

A chemical analysis is usually performed on only a small portion of the material to be

Muhwezi Godfrey,Chem Department pg. 10

3. Preparation of the laboratory sample for analysis

4- Obtaining a measured quantity of the sample

5- Solution of the sample

Muhwezi Godfrey,Chem Department pg. 11

6. Separation of interfering substances

7. The completion of the analysis

8. Calculation and interpretation of results

The conversation of the experimental data from an analysis to a concentration is ordinarily

Muhwezi Godfrey,Chem Department pg. 12

The Language of Analytical Chemists.

Qualitative analysis: An analysis in which we determine the identity of the constituent

Important chemical concepts