ANALYTICAL CHEMISTRY

CT 104

LECTURER: MRS N. P. ZINYAMA

 MODULE OUTLINE
ANALYTICAL CHEMISTRY-CT 104 MODULE OUTLINE 2017

• Outline
• Section A: The nature and scope of analytical
chemistry
• Analytical chemistry, its function and application
• Analytical problems and procedures
• Section B: Assessment of data
• Errors in analytical measurements
• Assessment of accuracy and precision
 MODULE OUTLINE
Section C: Analytical reactions in solution/ Classical techniques
Titrimetric reactions
• Overview
• Titration curves, Selecting and Evaluating the End point, Quantitative applications,
Evaluation of Titrimetric method
• Complexation
• Redox
• Acid-base
• Precipitation
Gravimetric reactions
• Overview
• Theory, Practice, Quantitative applications, Quantitative applications, Evaluation of
Gravimetric method
• Precipitation
• Volatilization
• Particulate
 MODULE OUTLINE
References
• Fundamentals of analytical chemistry, D.A
Skoog
• Journal of Chemical education
• Internet
 Assessment
• 2 Assignments 5%
• 2 Tests 10%
• 4 Practicals 25%
• End of semester exam 60%
 What is Analytical Chemistry?

Analytical chemistry seeks ever improved means of measuring the chemical

composition of natural and artificial materials
The techniques of this science are used to identify the substances which may
be present in a material and determine the exact amounts of the identified
substances
Study of methods for determining the composition of substances

Qualitative: (what) provides information about the identity of

an atomic, molecular or biomolecular species

Quantitative: (how much) provides numerical information as

to the relative amounts of species

Definitions from www.acs.org

Overview
 History of Analytical Methods

Classical methods: early years (separation of analytes) via precipitation, extraction or

distillation

Qualitative: recognized by color, boiling point, solubility, taste

Quantitative: gravimetric or titrimetric measurements

Instrumental Methods: newer, faster, more efficient

Physical properties of analytes: conductivity, electrode potential, light emission

absorption, mass to charge ratio and fluorescence, many more…
 The General Analytical Problem

Select sample
Extract analyte(s) from matrix

Separate analytes

Detect, identify and

quantify analytes

Determine reliability and

significance of results
Errors in Chemical Analysis

Impossible to eliminate errors.

How reliable are our data?
Data of unknown quality are useless!

•Carry out replicate measurements

•Analyse accurately known standards
•Perform statistical tests on data
 Mean N
Defined as follows:
 xi
i=1
x =
N

Where xi = individual values of x and N = number of replicate

measurements

Median
The middle result when data are arranged in order of size (for even
numbers the mean of middle two). Median can be preferred when
there is an “outlier” - one reading very different from rest. Median
less affected by outlier than is mean.
 Illustration of “Mean” and “Median”
Results of 6 determinations of the Fe(III) content of a solution, known to
contain 20 ppm:

Note: The mean value is 19.78 ppm (i.e. 19.8ppm) - the median value is 19.7 ppm
 Accuracy

Measurement of agreement between experimental mean and

true value (which may not be known!).
Measures of accuracy:

Absolute error: E = xi - xt (where xt = true or accepted value)

Relative error: x x
E  i t 100%
r x
t
(latter is more useful in practice)
 Characterizing experimental errors
Errors affecting accuracy
• Accuracy Is the closeness of the measurement to its true or
accepted value.
• Errors affecting accuracy are called systematic or
determinate errors
• Absolute error and relative errors are used to express
accuracy
• The difference between the measured value and the true
value.
• Some sources of determinate errors are +ve and other –ve,
some larger and some smaller and hence they have a
cumulative effect either +ve or –ve in accuracy.
 Sources of Systematic Error
1. Instrument Error
Need frequent calibration - both for apparatus such as
volumetric flasks, burettes etc., but also for electronic
devices such as spectrometers.
2. Method Error
Due to inadequacies in physical or chemical behaviour
of reagents or reactions (e.g. slow or incomplete reactions)
Example from earlier overhead - nicotinic acid does not
react completely under normal Kjeldahl conditions for
nitrogen determination.
3. Personal Error
e.g. insensitivity to colour changes; tendency to estimate
scale readings to improve precision; preconceived idea of
“true” value.
 Systematic errors can be
constant (e.g. error in burette reading -
less important for larger values of reading) or
proportional (e.g. presence of given proportion of
interfering impurity in sample; equally significant
for all values of measurement)
Minimise instrument errors by careful recalibration and good
maintenance of equipment.

Minimise personal errors by care and self-discipline

Method errors - most difficult. “True” value may not be known.

Three approaches to minimise:
•analysis of certified standards
•use 2 or more independent methods
•analysis of blanks
 Characterizing experimental errors
Errors affecting Precision
• Precision
• Refers to the reproducibility of
measurements or the closeness of results
measured in exactly the same way. In other
words, it is the grouping of data.
 Errors affecting Precision
• It can also be defined as a measure of spread
about a certain value
• It can be expressed as a range, standard
deviation or variance
 Errors affecting Precision
• There are 2 types of precision
i. Repeatability- precision when a single
analyst completes an analysis in a single
session using the same solutions, equipment
and instrumentation
ii. Reproducibility- precision under any set of
conditions, including different analysts and
between lab sessions for a single analyst
 Errors affecting Precision
• Errors affecting precision are indeterminate
and characterised by random variations in
magnitude and direction.
• Because indeterminate errors are random, +ve
and –ve indeterminate errors tend to cancel.
 Precision
Standard deviation
Precision

Variance
 Precision

Relative standard deviation

 Precision

Relative standard deviation

Illustrating the difference between “accuracy” and “precision”

Low accuracy, low precision Low accuracy, high precision

High accuracy, low precision High accuracy, high precision

Some analytical data illustrating “accuracy” and “precision”

HN NH3+Cl-
S
H H

Benzyl isothiourea
hydrochloride

OH

N
Analyst 4: imprecise, inaccurate
Analyst 3: precise, inaccurate Nicotinic acid
Analyst 2: imprecise, accurate
Analyst 1: precise, accurate
 Titrations
 Definition: an analytical technique that measures
concentration of an analyte by the volumetric addition of a
reagent solution (titrant)- that reacts quantitatively with the
analyte

 For titrations to be useful, the reaction must generally be

quantitative, fast and well-behaved

Advantages Disadvantages
great flexibility large amount of analyte required
suitable for a wide range of analytes lacks speciation (similar structure)
manual, simple colorimetric -subjective
excellent precision an accuracy sensitive to skill of analyst
readily automated reagents unstable
 Titration of strong acids and strong
bases
i. Write the reaction equation
ii. Calculate the volume of the reagent with the
unknown volume required to reach equilibrium
iii. Calculate the initial pH
iv. Determine the reagent in excess to determine
the structure of the equation
v. Add volumes of the reagent with the unknown
volume and calculate concentration and pH
 Titration of strong acids and strong
bases
v. Calculate the equilibrium pH
vi. Continue adding volumes of the reagent with
unknown volume and calculate the
concentration and pH
vii. Plot the titration curve