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Chemistry 331

Chapter 33 Automated Methods of Analysis.

33A AN OVERVIEW OF AUTOMATIC INSTRUMENTS AND

INSTRUMENTATION

By IUPAC terminology, automatic devices do not modify their operation as

a result of feedback from an analytical transducer. For example, an

automatic acid/base titrator adds reagent to a solution and simultaneously

records pH as a function of volume of reagent. In contrast, an automated

instrument contains on or more feedback systems that control the course of

the analysis. Thus, some automated titrator compare the potential of a glass

electrode to its theoretical potential at the equivalence point and use the

difference to control the rate of addition of acid or base.

33A-1 Advantages and Disadvantages of Automatic Analyses

In the proper context, automated instruments offer a major economic

advantage because of their savings in labor costs. A second major advantage

of automated instruments is their speed, which is frequently significantly

greater than that of manual devices. The third advantage of automation is

that a well-designed analyzer can usually produce more reproducible results

over a long period of time than can an operator employing a manual

instrument. The reasons for this are machines do not suffer from fatigue,

which has been demonstrated to adversely affect the result obtained

manually, particularly near the end of a working day. The second reason is

the high reproducibility of the timing sequences of automated instruments.

33A-2 Unit Operations in Chemical Analysis

All analytical methods can be broken down into a series of eight steps, or

unit operations, any one of which can be automated. The table below list the

steps in the order in which they occur in a typical analysis.

33A-3 Types of Automatic Analytical Systems

Automatic analytical systems are of two general types: discrete analyzers

and continuous-flow analyzers; occasionally, a combination of the two is

encountered. In a discrete instrument, individual samples are maintained as

separate entities and kept in separate vessels throughout each unit operation

listed on the table. In continuous-flow systems, in contrast, the sample

becomes a part of a flowing stream where the several unit operations take

place as the sample is carried from the injection or sample introduction point

to a flow-through measuring unit, and thence to waste. Both instruments are

computer controlled.

33B FLOW-INJECTION ANALYSIS

Flow-injection methods, in their present form, were first described in the

mid 70s. Flow-injection methods are and outgrowth of segmented-flow

procedures, which were widely used in clinical laboratories in the 1960s and

1970s for automatic routine determination of a variety of species in blood

and urine samples for medical diagnostic purposes. The discoverers of flow-

injection analysis found, however, that excess dispersion and cross-

contamination are nearly completely avoided in a properly designed system

without air bubbles and that mixing of samples and reagents could be easily

realized.

33B-1 Instrumentation
Sample and Reagent Transport System

Ordinarily, the solution in a flow-injection analysis is moved through the

system by a peristaltic pump, a device in which a fluid ( liquid or gas) is

squeezed through plastic tubing by rollers.

Sample Injectors and Detectors

The injectors and detectors employed in flow-injection analysis are similar

in kind and performance requirements to those used in HPLC. For successful

analysis, it is vital that the sample solution be infected rapidly as a pulse or

plug of liquid; in addition, the injections must not disturb the flow of the

carrier stream. Detection in flow-injection procedures has been carried out

by atomic absorption and emission instruments, fluorometers,

electrochemical systems, refractometers, spectrophotometers, and

photometer.

Separations in FIA

Separations by dialysis, by liquid/liquid extraction, and by gaseous diffusion

are readily carried out automatically with flow-injection systems.

Dialysis and Gas Diffusion

Dialysis is often used continuous-flow methods to separate inorganic ions,

such as chloride or sodium or small organic molecules, such as glucose,

from high-molecular-weight species such as proteins.

Extraction

Another common separation technique readily adapted to continuous-flow

methods is extraction. It is important to reiterate that none of the separation

procedures in FIA methods is ever complete. The lack of completeness is of

no consequence, however, because unknowns and standards are treated an

identical way.

33B-2 Principles of Flow-Injection Analysis

Dispersion

Dispersion D is defined by the equation

D = co/c

Where co is the analyte concentration of the injected sample and c is the

peak concentration at the detector. Dispersion is influenced by three

interrelated and controllable variables: sample volume, tube length, and

pumping rate.

33B-3 Applications of Flow-Injection Analysis

In the flow-injection literature, the terms limited dispersion, medium

dispersion, and large dispersion are frequently encountered where they refer

to dispersions of 1 to 3, 3 to 10, and greater than 10, respectively.

Limited-Dispersion Applications

Limited-dispersion flow-injection techniques have found considerable

application for high-speed feeding of such detector systems as flame atomic

absorption and emission as well as inductively coupled plasma. It is also

used with electrochemical detectors such as specific-ion electrodes and

voltammetric microelectrodes.
33C DISCRETE AUTOMATIC SYSTEMS

A wide variety of discrete automatic systems are offered by numerous

instrument manufacturers. Some of these devices are designed to perform

one or more.

33C-1 Automatic Sampling and Sample Definition of Liquids and Gases

Several dozen automatic devices for sampling liquids and gases are currently

available from instrument manufactures. This device consists of a movable

probe, which is a syringe needle or a piece of fine plastic tubing supported

by an arm that periodically lifts the tip of the needle or tube form the sample

container and positions it over a second container in which the analysis is

performed.

33C-2 Robotics

With solids, sample preparation, definition, and dissolution involves such

unit operations as grinding, homogenizing, drying, weighing, igniting,

fusing, and treating with solvents.

The robotic system is controlled by a microprocessor that can be instructed

to bring samples to the master laboratory station where they can be diluted,

filtered, partitioned, ground, centrifuged, extracted, and treated with

reagents. The device can also be instructed to heat and shake samples,
dispense measured volumes of liquids, inject samples into a

chromatographic column, and collect fractions from a column.

33D ANALYSES BASED UPON MULTILAYER FILMS

During the past two decades, a technology has been developed for

performing the various steps in a quantitative analysis automatically in

discrete films arranged in multilayers supported on transparent, disposable

plates having the size of a postage stamp.

The cost of such instruments is large, which has required their location in

centralized laboratories, where their expense can be amortized over a large

volume of samples. The advent of multi-layer film elements means that it is

now economic to perform some of these routine clinical analyses

automatically in decentralized locations.

Useful Websites Dealing With Instrumental Analysis

Chemical Abstracts Service:

http://www.cas.org

Chemical Center Home Page:

http://www.chemcenter/org

Journal of Chemistry and Spectroscopy:

http://www.kerouac.pharm.uky.edu/asrg/wave/wavehp.html

The Analytical Chemistry Springboard at Umea U.

http://www.anachem.umu.se/jumpstation.htm
Comprehensive Info on HPLC
http://hplc.chem.vt.edu/

Analytical Instrumentation Group.

http://www.ch.kcl.ac.uk

Precision Instruments and Mechanology.

http://www.tsinghua.edu.cn/docse/yasz/thdpim.html

Instrument and Controls.

http://www.osmonics.com/products/page394.htm