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Analytical Notes

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Qualitative analysis reveals the identity of the elements and compounds in a sample.

Quantitative analysis indicates the amount of each substance in a sample.


Analytes are the components of a sample that are determined.

QuANTiTATive ANAlyTiCAl meThods


gravimetric methods, we determine the mass of the analyte or some compound chemically
related to it
In a volumetric method, we measure the volume of a solution containing sufficient reagent to
react completely with the analyte
electroanalytical methods, we measure electrical properties such as potential, current,
resistance, and quantity of electrical charge
In spectroscopic methods, we explore the interaction between electromagnetic radiation and
analyte atoms or molecules or the emission of radiation by analytes
miscellaneous methods, we measure such quantities as mass-to-charge ratio of ions by mass
spectrometry, rate of radioactive decay, heat of reaction, rate of reaction, sample thermal
conductivity, optical activity, and refractive index.

Precision describes the reproducibility of measurements—in other words, the closeness of


results that have been obtained in exactly the same way.

Three terms are widely used to describe the precision of a set of replicate data: standard
deviation, variance, and coefficient of variation. These three are functions of how much an
individual result xi differs from the mean, called the deviation from the mean di.

Accuracy indicates the closeness of the measurement to the true or accepted value and is
expressed by the error

Note that accuracy measures agreement between a result and the


accepted value. Precision, on the other hand, describes the agreement among several results
obtained in the same way. We can determine precision just by measuring replicate samples.

The absolute error of a measurement is the difference between the measured value and the
true value. The sign of the absolute error tells you whether the value in question is high or low. If
the measurement result is low, the sign is negative; if the measurement result is high, the sign is
positive.
The relative error of a measurement is the absolute error divided by the true value. Relative
error may be expressed in percent, parts per thousand, or parts per million, depending on the
magnitude of the result.

Relative error is also expressed in parts per thousand (ppt). For example

random (or indeterminate) error, causes data to be scattered more or less symmetrically around
a mean value.Random, or indeterminate, errors affect measurement precision.

systematic (or determinate) error, causes the mean of a data set to differ from the accepted
value.Systematic, or determinate, errors affect the accuracy of results.
Sources of Systematic Errors
There are three types of systematic errors:
■Instrumental errors are caused by non ideal instrument behavior, by faulty calibrations, or by
use under inappropriate conditions.
■ Method errors arise from nonideal chemical or physical behavior of analytical systems.
■ Personal errors result from the carelessness, inattention, or personal limitations of the
experimenter.

A population is the collection of all measurements of interest to the experimenter


while a sample is a subset of measurements selected from the population.
The confidence interval for the mean is the range of values within which the population mean m
is expected to lie with a certain probability.
The confidence level is the probability that the true mean lies within a certain interval and is
often expressed as a percentage.
Describe in your own words why the confidence interval for the mean of five measurements is
smaller than that for a single result.
Discuss how the size of the confidence interval for the mean is influenced by the following (all
the other factors are constant): (a) the standard deviation s. (b) the sample size N. (c) the
confidence level.

A conjugate base is formed when an acid loses a proton. For example, acetate ion is the
conjugate base of acetic acid. Similarly, ammonium ion is the conjugate acid of the base
ammonia.
A conjugate acid is formed when a base accepts a proton.
the common strong bases include NaOh, KOh, Ba(Oh)2, and the quaternary ammonium
hydroxide r4NOh, where r is an alkyl group such as Ch3 or C2h5.

the common strong acids include hCl, hBr, hI, hClO4, hNO3, the first proton in h2SO4, and the
organic sulfonic acid rSO3h.
A standard solution is a reagent of known concentration. Standard solutions are used in
titrations and in many other chemical analyses
Back-titration is a process in which the excess of a standard solution used to consume an
analyte is determined by titration with a second standard solution. Back-titrations are often
required when the rate of reaction between the analyte and reagent is slow or when the
standard solution lacks stability.
The equivalence point is the point in a titration when the amount of added standard reagent is
equivalent to the amount of analyte.
The end point is the point in a titration when a physical change occurs that is associated with
the condition of chemical equivalence.

A primary standard is an ultrapure compound that serves as the reference material for a titration
or for another type of quantitative analysis.

A secondary standard is a compound whose purity has been determined by chemical analysis.
The secondary standard serves as the working standard material for titrations and for many
other analyses.

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