General Concepts

and
Experimental Error
Harris (8
th
Edition)
Chapter 3 => p. 51 - 67
Section 1
1
1.1 I ntroduction

Analytical Chemistry = separating, identifying, and determining the
relative amounts of components in sample of matter.

Two main areas of analytical chemistry:

Qualitative Analysis: reveals chemical identity.
- What elements or compounds present?

Quantitative Analysis: establishes relative amount of species
(analytes) in numerical terms.
- How much of substance is present?

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From: Analytical Chemistry, Gary D. Christian, John Wiley & Sons, 2004
Classification of Analytical Methods

Two classes:
(i) Classical or wet-chemical methods (ii) Instrumental methods

(i) Classical or wet-chemical methods
- Group of analytical methods that only requires the use of chemicals,
a balance, calibrated glassware, and other commonplace apparatus
such as funnels, burners or hot plates, flasks, and beakers.

Qualitative identification by colour, indicators, boiling points, odours.
Quantitative mass (e.g., gravimetric) or volume (e.g., volumetric analyses).


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(ii) Instrumental methods
- Analytical methods that requires the use of an analytical instrument
in addition to the apparatus used for classical analyses.

Qualitative identification by measuring physical property
Examples:
Spectroscopy =>
Electrochemistry =>
Chromatography =>
Capillary electrophoresis =>

Quantitative measuring property and determining relationship to
concentration
Examples:
Spectrophotometry =>

Mass spectrometry =>

Chromatography =>
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Calibration of Analytical Instrument

1. Prepare a number of standard solutions of increasing concentrations
e.g., 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M

2. Measure a quantitative property (e.g., absorbance) for all solutions using
the instrument.

Example:







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3. Plot a curve for the values (Absorbance versus Concentrations)
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Selecting an Analytical Method

What accuracy is required?


How much sample is available?


What is the concentration range of the analyte?



What components of the sample will cause interference?


What are the physical and chemical properties of the sample matrix?

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Flow Diagram of the Steps in Quantitative Analysis
1.2 Basic Concepts

Significant Figures for Mixed Operations
Mixed operations are mathematical computations that involve
subtraction/addition and multiplication/division.
Convert all numbers into scientific notation and do the computation.
Express the answer to conform to the number with the least number
of significant figures.

Example:













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Logarithms and Antilogarithms

For an expression: n = 10
a
, the base 10 logarithm of n is the number a.
i.e., n = 10
a
means log n = a
n is referred to as the antilogarithm of a

A logarithm is composed of two parts:
Characteristic: integer part Mantissa: decimal part






Number of digits in mantissa of log x = number of significant figures in x.







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Chemical Concentrations

Molarity and Molality

- Molarity (M): concentration expressed as number of moles of substance
per liter of solution.
It also expresses number of millimoles of a solute per milliliter of solution.



Molality (m): concentration expressed as moles of substance per
kilogram of solvent (not total solution).




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Molarity changes with temperature because the volume of a solution
changes with temperature since volume depends on density, a
temperature dependent property.

Molality is independent of temperature.
Formal Concentration (F)

- Number of moles of solute, regardless of chemical form, per liter of solution.
- Used for solutions of ionic salts that do not exist as molecules in the solid or in
the solution i.e., strong electrolytes, that ionize.
e.g.,
- It is numerically equal to molarity if the substance dissolve without dissociating
into ions.
e.g.,





- For substances that ionize in solution, molarity and formality are different.


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Percent Composition

- Three forms:
(i) Weight percent (wt %; % w/w)
(ii) Volume percent (vol %; % v/v)
(iii) Weight-to-volume percent (% w/v)

- All are expressed as units of solute per 100 units of sample.

(i) Weight percent (wt %; % w/w)
- Grams of solute per 100 g of solution.






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(ii) Volume percent (vol %; % v/v)
- Milliliters of solute per 100 mL of solution.









(iii) Weight-to-volume percent (% w/v)
- Grams of solute per 100 mL of solution.




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Part Per Thousand, Part Per Million and Part Per Billion

(i) Part per thousand (ppt or %) grams of substance per thousand
of total solution or mixture.





(ii) Part per million (ppm) grams of substance per million of total
solution or mixture.






(iii) Part per billion (ppb) grams of substance per billion of total
solution or mixture.



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1 g of water is considered approximately equal to 1 mL of water.

Thus, ppm and ppb can be expressed as:














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Summary
Units used
Name Abbreviation w/w w/v v/v
Part per thousand or ppt mg/g mg/mL mL/L
Part per million ppm mg/g mg/mL nL/mL
mg/kg mg/L mL/L
Part per billion ppb ng/g ng/mL nL/L
mg/kg mg/L
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Conversion of Concentrations

(1) Converting ppb into molarity
A water sample contains 15.0 ppb MgCO
3
. Calculate the molarity of the
MgCO
3
solution.
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(2) Conversion into ppm
A 50.0-mL serum sample contains 5.34 x 10
5
g glucose. Calculate the
concentration of glucose in ppm.



















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(3) Conversion of ppm to molarity of ion
What is the molarity of K
+
in a solution that contains 32.5 ppm K
3
Fe(CN)
6
?
[K
3
Fe(CN)
6
= 329.3 g/mol].

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(4) Preparation of solution containing ppm of an ion
(a) Calculate the molar concentration of 2.00 ppm solutions each of Li
+
and Pb
2+
.
(b) What weight of Pb(NO
3
)
2
will have to be dissolved in 1 liter of water to
prepare 200 ppm Pb
2+
solution?

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(5) Conversion of wt % into molarity and molality
Concentrated HCl (MW 36.46) has a density of 1.19 g/mL and is 37.0 wt% HCl.
Calculate the molarity and molality for this acid.
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Precision and Accuracy

Precision
- A measure of the reproducibility of the method.
How close the results, obtained in the same way, are.




- Usually expressed as a percent relative standard deviation, % RSD.




Accuracy
- Indicates how close a measured value is to the true value.


- Normally expressed as the relative percent error.
A 1% error indicates that a measured concentration is within 1% of
the true analyte concentration.


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Example:
Absolute Uncertainty and Relative Uncertainty

Absolute Uncertainty
- indicates the margin of uncertainty associated with a measurement.

Example:




Relative Uncertainty
- compares the magnitude of the absolute uncertainty with the magnitude
of its associated measurement.

Example:



- When expressed as a percentage, it is referred to as percent
relative uncertainty.



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1.3 Types of Error in Experimental Data

Two main types:
(i) Systematic error
(ii) Random error


(i) Systematic error
- Also called Determinate error.
- Error is either high every time or low every time.
- Causes mean of a set of data to differ from accepted value.
affects accuracy of result.

- Originates from a flaw in equipment or the design of an experiment.
- Key feature of this error is that it is reproducible.
- Definite causes (sources) can be identified and eliminated.
Statistics not used here.

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Examples:
Incorrect standardization of a pH meter.








Uncalibrated buret






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(ii) Random error

- Also called Indeterminate error.
- Produces a value that sometimes is high and sometimes is low.

- Originates from effects of uncontrolled variables in a measurement,
and thus, it is always present.

- Random errors follow a normal distribution, or a Gaussian curve.










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- Causes data to be scattered more or less symmetrically around
mean value of the normal distribution.
affects precision of measurement.
- Not readily discovered and not eliminated
Statistics used.
Hence it is taken into account when reporting analytical results.
Repeated measurement of same quantity can reduce it.


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Note:

Example:
Flipping coins
- appearance of heads or tails is a random event.
- distribution follows a Gaussian or Normal curve
- a coin was flipped ten times by 395 students over a 13-year period
1.4 Propagation of Uncertainty

- It could occur from two sources:
From random error
From systematic error
From Random Error

- In an analysis, the greater the number of measurement steps we take,
the less certain we become of the true measurement.

- Each of the uncertainties contributes its part to the final, larger
possible uncertainty.

- Since each of the uncertainties is carried along to the final measurement,
the process is called propagation of uncertainty.
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Three rules to follow:

(i) For addition and subtraction, the absolute error is used in calculations.


(ii) For multiplication and division, the relative error is used in calculations.


(iii) All the terms of a sum must be of only one type: either absolute
or relative error values.
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Exponents and Logarithms

(i) Uncertainty for powers and roots
















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(ii) Uncertainty for logarithm
- Relative uncertainty, not percent relative uncertainty, is used in calculations.
=> Because one side of equation has relative uncertainty and the other has
absolute uncertainty.









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(iii) Uncertainty for natural logarithm
- Relative uncertainty, not percent relative uncertainty, is used in calculations.










(iv) Uncertainty for 10
x











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(v) Uncertainty for e
x






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(vi) Uncertainty in H
+
concentration
Example: For pH = 5.21 0.03, find [H
+
] and its uncertainty.
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From Systematic Error

- Two common examples are encountered in Chemistry.

(i) Uncertainty in Molecular Mass

- The uncertainty is hardly from random error in measuring the
atomic mass.
- It is mainly from isotopic variation in samples of oxygen from
different sources.

Example 1: Identical atoms
- Uncertainty in mass of n identical atoms = n x (uncertainty in atomic mass).

Consider the atomic mass of oxygen = 15.9994 0.0003 g/mol.
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Example 2: Non-identical atoms
- For C
2
H
4



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(ii) Multiple Deliveries from One Pipet

- Consider a 25-mL volumetric pipet which is certified by manufacturer to
deliver 25.00 0.03 mL.

- The volume delivered by such a pipet is reproducible but it can lie within the
range 24.97 to 25.03 mL.

- Difference between 25.00 mL and the actual volume delivered by the pipet is
a systematic error.




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