Thermo Gravimetric Analysis –source of

Errors

Systematic and Random Errors of Measurement

Systematic and random errors constitute the difference between a true value and an individual
measurement. An example of systematic error in TGA is buoyancy. Systematic error can be
rectified by carrying out a blank measurement. The result of the blank run is subtracted from the
sample measurement. An example of random errors, also known as indeterminate errors, is the
measurement of enthalpy of fusion.

Precision, Trueness and Accuracy

Accuracy is defined as the closeness of agreement between an individual value and a

true value. Accurate results are free from systematic and random errors and accuracy
also involves trueness and precision.

Precision is defined as the closeness of agreement between individual values. If the

random error is small better precision can be achieved.

Trueness is described as the closeness of agreement between the mean value of a

measurement series and the true value. The smaller the systematic error, the better the
trueness of an analytical method.

Important Sources of Measurement Errors

Several factors contribute to systematic and random measurement errors in thermal

analysis. The significant ones are listed below

 Influence of the procedure

 Instrumental influences
 Sampling and sample preparation
 Environmental influences
 Experimental parameters
 Evaluation methodology
 Time-dependent factors
  Shortcomings of the operator
 Gross errors

The above factors are detailed in the following sections.

Influence of the Procedure

Different analytical procedures give different results. Figure 4 shows the measurement
of Solid Fat Index using DSC and NMR.

Figure 3. Determination of the Solid Fat Index (SFI) by DSC and NMR.

Instrumental Influences

A common cause for systematic errors in measurement is improper adjustment of the

instrument used for the measurement.

Sample Preparation

Sample selection and preparation is a major step in thermal analysis. Measurement

errors can occur if the following factors are overlooked:
  Changes in the sample due to stress
 Change in the material properties over time, during storage or transport
 Instability or contamination of the sample
 Inaccurate sample weighing
 Inaccurate determination of the sample geometry

Figure 5 shows a good sampling plan, which follows the definition of consistent
sampling process.

Environmental Influences

The measuring system should be insensitive to influences of its environment. In thermal

analysis, the key factors affecting the measurement signal are given below:
  Pressure
 Temperature
 Vibrations
 Contamination

Method Parameters and Evaluation

Conditions, such as sample mass, sample geometry, heating and cooling rate,
atmosphere, temperature range, crucible, force, pressure, displacement and frequency,
sampling and sample preparation and storage, in which a measurement is carried out
must be monitored for each measurement.

Time-Dependent Factors

Time is another key factor that affects measurement errors in a systematic way. For
example, a sensor’s sensitivity can change over time.

Shortcomings of the Operator

Individual abilities, practical skills, experience and theoretical knowledge of the operator
also influence systematic and random errors of measurement.

Gross Errors

Gross errors are a third type of errors mainly comprising the following:

 Wrongly transcribed results and measurement data

 Signs and rounding
 Errors in calculations
 Programming errors in computer programs
 Incorrect weighing or determination of sample geometry
 Mistaken identity of sample material or wrong reagent concentrations.

Detection and Elimination of Measurement Errors

Systematic errors of measurement can be detected using comparative measurements.

The three major comparative measurements are listed below:
  Deliberate change of the experimental parameters
 Use of a fundamentally different measuring method
 Interlaboratory studies (Round Robin studies)

Conclusions

Trueness and precision are a measure of the systematic and random errors of
measurement, respectively. The important causes of errors in measurement are
influences of the procedure, instrumental influences, environmental influences,
sampling and sample preparation, experimental parameters, shortcomings of the
operator, evaluation methodology, and time-dependent factors. The accuracy of
analytical methods can be enhanced by having a broad understanding of the
measurement procedures and method development in a competent manner.