INSMETH

Lecture 1: Introduction
Maam Glenn Medina De La Salle University
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Areas of Analytical Chemistry

QUALITATIVE - identification of substances present in a sample. This area includes structural elucidation. QUANTITATIVE - determination of the relative concentration or amount of a particular substance or chemical species often referred to as the chemical constituent or analyte.
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What is Analytical Chemistry?

A measurement science consisting of a set of powerful methods applied throughout industry, medicine and other aspects of science. It involves qualitative and quantitative analyses which reveal the identity and amount of each substance in a sample, respectively.
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Instrumental Methods of Analysis Pertain to the application of instrumental methods to chemical analysis including electrochemical, spectrophotometric and chromatographic analysis.

Instrumental Methods of Analysis

Techniques:
1. Method Development 2. Sample Collection 3. Sample preparation Defining Replicate Samples, Dissolving the Samples, Eliminating interferences 4. Optimization 5. Analysis Measuring the amount of analyte, Calculating the concentration, Reliability of the data
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The role of Analytical Chemists

To ensure quality of a product/service through the aid of chemical instruments/stand ard analysis protocols
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THE ANALYTICAL PROCESS An analytical process does not only involve the actual performance of the experiment but actually starts with the planning and ends with the reporting of the result.

Quantitative Analytical Methods 1. 2. 3. 4. Gravimetric Volumetric Electroanalytical Spectroscopic

Quantitative Chemical Analysis

Chemical Sample Additional Data Analytical Technique
Classical or Instrumental

Analyte Concentration

Measurement Data
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Steps in Quantitative Analysis

1. 2. 3. 4. 5. 6. 7. 8. 9. Formulating the Question Method selection Sample Collection Sample Processing Eliminating interferences Calibration, Measurement Calculations Evaluation of Results Conclusions

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1. Formulating the question

The analytical process depends on the set of problems or things that the analyst wants to know and on the type of sample that will be subjected to the analysis.

2. METHOD SELECTION
The nature of the analyte and the extent of analysis are determined.
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3. SAMPLING (SAMPLE COLLECTION)

The process by which a representative fraction of the sample is acquired The most difficult step in the entire analytical process. The step that limits the accuracy of the procedure (eg sampling of lakewater; soil or animal tissue)
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4. SAMPLE PROCESSING (PREPARATION)

Water is a common component present in samples. Thus, analysis can be conducted on Dry basis. Moisture in the sample is removed before weighing. The sample can be dried at ambient temperature (air drying) or by heating to a temperature > 105C.
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4. SAMPLE PROCESSING (PREPARATION)

On an as received or wet basis. The moisture content of the sample is determined upon the receipt of the sample. Representative sample obtained; weight loss determined after drying. The rest of the sample is dried and all analyses are performed. The corresponding correction is made due to the moisture content.

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4. SAMPLE PROCESSING (PREPARATION)

The sample and the analyte must be in solution. For insoluble samples, it is necessary to use more drastic conditions to decompose and/or dissolve them.

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4. SAMPLE PROCESSING (PREPARATION)

Decomposition/Dissolution of Samples: 1. concentrated HCl 2. hot concentrated HNO3 3. hot concentrated H2SO4 4. HClO4 (NOTE: EXPLOSIVE when hot/concd)
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4. SAMPLE PROCESSING (PREPARATION)

Decomposition/Dissolution of Samples: 5. Aqua regia (1HNO3 : 3HCl) 6. HNO3-HClO4 7. HF 8. Fluxes - sample is mixed with an alkali metal salt (flux) and fused to form a water-soluble product called a melt by heating to a high temperature (300-1000C) 9. Ashing (Dry or Wet)

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5. ELIMINATING INTERFERENCES
Interference the presence of a substance changes the signal in the analysis of another substance 1. Adjustment of the conditions within the solution 2. Usage of blank to compensate for their effect 3. Precipitating the interference due to differences in solubility

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6. QUANTITATIVE MEASUREMENT
Calibration is done to ensure accuracy in the results. All measurements depend on the relationship between concentration of the analyte and a physical or chemical property of the analyte.
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6. QUANTITATIVE MEASUREMENT
The choice of the analytical method to adopt for an analysis may depend on the Absolute Methods Relative Methods

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6. QUANTITATIVE MEASUREMENT Absolute Methods

rely upon accurately known fundamental constants (e.g. Molar Mass) for calculating the amount of analyte

Example: Gravimetric Method

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6. QUANTITATIVE MEASUREMENT
Relative Methods
require comparison against some solution of known concentration

Examples: Titrimetric Method, Electrochemical Method, Instrumental Method

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7. CALCULATIONS/INTERPRETATION OF DATA 8. EVALUATION OF RESULTS

All analyses conducted in replicates. Statistical treatment of the results necessary. Uncertainties in measurements cause the replicate values to differ with one another and these cause the values to scatter. The experimental error is classified as either (a) systematic error or determinate error and (b) random error or indeterminate error.

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Classical vs Instrumental Techniques

Classical analysis
signal depends on the chemical properties of the sample a reagent reacts completely with the analyte the relationship between the measured signal and the analyte concentration is determined by chemical stoichiometry
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Classical vs Instrumental Techniques

Instrumental analysis
physical property is measured by the instrument, such as the electrical potential or the ability of the sample to absorb light capable of detecting individual atoms or molecules in a sample analysis at the ppm (g/mL) and even ppb (ng/mL) level
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Advantages of instrumental methods

Trace analysis Large numbers of samples analyzed quickly Automation Less skill and training required

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Classification of Instrumental analysis

1. Electrochemical methods of analysis
- analyte participates in a redox reaction or other process potentiometric analysis
analyte is part of a galvanic cell, which generates a voltage; magnitude of the voltage depends on the concentration of analyte

voltammetric analysis
analyte is part of an electrolytic cell; magnitude of the current is directly proportional to the concentration of analyte
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Classification of Instrumental analysis

2. Spectrochemical methods of analysis
analyte interacts with electromagnetic radiation absorption-based techniques
based on the measurement of the amount of light absorbed by a sample
atomic absorption molecular absorption NMR

emission-based techniques
generally based on the measurement of light emitted or scattered by a sample
atomic emission molecular fluorescence
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Classification of Instrumental analysis

3. Mass spectroscopy
analyte is ionized and subsequently detected most important use of mass spectrometers in quantitative analysis is as a gas or liquid chromatographic detector. A more recent innovation is the use of an inductively coupled plasma (ICP) as an ion source for a mass spectrometer; this combination (ICP-MS) is a powerful tool for elemental analysis.
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Classification of Instrumental analysis Chromatography and Electrophoresis separate a chemical sample into its individual components, which are then typically detected by one of the methods listed above.
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Classification of Instrumental analysis

(based on stoichiometry)

Electrogravimetry, and potentiostatic and amperostatic coulometry relatively sophisticated classical methods that have a significant instrumental component

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CALIBRATION
Involves the use of a set of standard solutions which enables the determination of the analyte concentration BLANK SAMPLE a solution whose matrix is the same as the standard solutions in the absence of the analyte

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DETECTION LIMIT
The smallest quantity of analyte that is significantly different from a blank Also known as Limit of Detection or LOD

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Statistical Treatment of Analytical Data

Mean/Average = x / n Median middle result when replicate data are arranged according to increasing or decreasing value Mode the value that occurs most frequently Absolute Error: E = Xi - Xt Relative Error: Er = (Xi - Xt / Xt) x 100% Deviation: d = IXi - meanI Relative deviation: dr = (d / mean) x100 Standard deviation: (x i x )2
s = n 1

Relative Standard Deviation: RSD = s/mean Coefficient of Variation: CV = RSDx100

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