ANALYTICAL CHEMISTRY • Proximate or Partial – determine only a

limited number of the specie in the sample

• Ultimate – determines the amount of each
element in the sample regardless of
LECTURE 1. THE NATURE OF ANALYTICAL CHEMISTRY composition
• Complete – determines the amount of each
What is Analytical Chemistry?
element in the sample present per
Analytical chemistry is concerned with the chemical composition
characterization of matter, both qualitative (what is it) and • Destructive – ends up consuming the sample
quantitative (how much is it). or renders it unusablef or the succeeding
analyses; common in wet analyses
Chemicals make up everything we use or consume, and • Non-destructive – renders the sample usable
knowledge of the chemical composition of many for the succeeding analyses
substances is important in our daily lives.
THE ANALYTICAL PROCESS
Qualitative and Quantitative Analysis

Qualitative Analysis
• Define the Problem
• establishes the chemical identity of the species in • -Once the problem is defined this will dictate how
the sample the sample is to be obtained, how much is
• identification of elements, ions or compounds needed, how sensitive the method must be, how
present in a sample accurate and precise it must be, and what
separations may be required to eliminate
Example: the presence of gunpowder residue on a hand interferences.
• Select a Method
Qualitative tests can be:
Two types of analytical methods:
• Selective tests or reactions- one that can occur with other
substances but exhibits a degree of preference for the Wet (Analysis) Chemistry Instrumental Methods
substance of interest • Also called Classical Uses sophisticated instruments
Analysis capable of measuring analyte’s
• Specific tests or reactions- one that occurs only with the • usually carried out in physical and chemical properties
substance of interest. liquid phase, and thus, it
was named wet
Quantitative Analysis – determination of how much of one
chemistry
or more constituents is present Example: the percent Example: Quantitative: gravimetry, spectrophotometer
undesired sulfur impurity present in coal titrimetry Qualitative: flame,
chromatography, and functional
Analyses may be:
group tests
Classified according to the amount of the
analyte/constituent present:
• Obtain a representative sample
• Trace – less than 0.01% • A chemical analysis is usually performed on only a
• Minor – 0.01 to 1.00% small portion of the material to be characterized.
• Major – beyond 1.00% • Grab sample - A grab sample is a single sample
collected at a specific time and location,
Classified according to the size of the sample representing a snapshot of the composition of a
substance or mixture at that particular moment.
• Macro – beyond 100 mg (or 100 microliters)
a) The gross sample consists of several portions of
• Semi-Micro – 10 to 100 mg (or 50-100
the material to be tested.
microliters)
b) The laboratory sample is a small portion of this,
• Micro – 1.0 to 10 mg (<50 microliters)
taken after homogenization.
• Ultra-micro – less than 1.0mg
c) The analysis sample is that actually analyzed.
Analyses may be:
Handling and storing samples
Classified according to the purpose

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Reviewer by: Jhecee Meir Tango BsCHE-1A

 Certain precautions should be taken in handling and storing
samples to prevent or minimize contamination, loss,
decomposition, or matrix change. In general, one must
prevent contamination or alteration of the sample by
1) the container,
2) the atmosphere
3) heat/temperature, or
4) light.
A solid laboratory sample is ground to decrease particle
size, mixed to ensure homogeneity and stored for various
lengths of time before analysis begins. A liquid and gaseous
sample must be kept inside a second sealed container.
• Prepare the Sample for Analysis
• The first step in analyzing the sample is to
measure the amount being analyzed (volume or
weight of the sample)
• Most analyses are performed on replicate
samples whose masses or volumes have been
carefully determined by careful measurements
with an analytical balance or with a precise
volumetric device.
*Replicates or replicate samples – portions of a material of
approximately the same size that are carried through an
analytical procedure at the same time and way
• Perform any necessary chemical separations
Interference or interferent – a species that causes an error
in an analysis by enhancing or attenuating (making smaller)
the quantity being measured
It is preferable to separate the analyte away from the
sample matrix, in order to minimize losses of the analyte.
Separation steps may include precipitation, extraction into
an immiscible solvent, chromatography, dialysis, and
distillation.
• Perform the Measurement
• Calibration is defined as the process of
assessment and refinement of the accuracy
and precision of a method, and particularly
the associated measuring equipment (i.e.,
an instrument), employed for the
quantitative determination of a sought-after
analyte
• A control is a sample that contains a known
amount of the substance you're testing for.
• A blank is a sample that does not contain the
substance you're testing for. It helps identify
and account for any contamination or
interference in your analysis.
• Calculate the Results and Report
Reviewer by: Jhecee Meir Tango BsCHE-1A
Computing analyte concentrations from
experimental data is usually relatively easy,
particularly with computers.
These computations are based on the raw
experimental data collected in the measurement
step, the characteristics of the measurement
instruments, and the stoichiometry of the
analytical reaction.
• Evaluating results by estimating reliability
• Analytical results are complete when their reliability
has been estimated. The experimenter must provide
some measure of the uncertainties associated with
computed results if the data are to have any value.
• The analyst should critically evaluate whether the
results are reasonable and elate to the analytical
problem as originally stated.
LECTURE 2. CALCULATIONS IN ANALYTICAL
CHEMISTRY
Moles
• SI unit for the amount of a chemical
substance
• 1 mole contains exactly 6.022x1023
(Avogadro’s constant) elementary entities
(atoms, molecules, ions, electrons, and so
on)
• Molecular weight (MW) - defined as the sum of the
atomic weights of the atoms that make up a compound
• Formula weight - a more accurate description for
substances that don’t exist as molecules but exist as ionic
compounds (strong electrolytes—acids, bases, salts)
• Molar mass - sometimes used in place of formula weight
CONCENTRATIONS OF SOLUTIONS
• Molarity (M) – the most widely used
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝑴𝒐𝒍𝒂𝒓𝒊𝒕𝒚 =
𝑳 𝒐𝒇 𝒔𝒐𝒍𝒏
In analytical chemistry, we normally work with milliliters in
titrations.
𝒎𝒊𝒍𝒍𝒊𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝑴𝒐𝒍𝒂𝒓𝒊𝒕𝒚 =
𝒎𝑳 𝒐𝒇 𝒔𝒐𝒍𝒏
• Formality (F) – numerically the same as
molarity but the term is used for solutions of
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 ionic salts that do not exist as molecules in Concentrations of Solid Samples
the solid or in the solution
• Molality (m) – temperature independent Calculations for solid samples are based on weight. The
concentration, convenient for general formula for calculating percent on weight/weight
physicochemical measurements of the basis:
colligative properties of substances such as %
𝒘𝒕 𝒘𝒕 𝒔𝒐𝒍𝒖𝒕𝒆 (𝒈) 𝒔𝒐𝒍𝒖𝒕𝒆
freezing point depression, vapor pressure 𝒈
%( ) = ( ) 𝒙𝟏𝟎𝟐( )
𝒘𝒕 𝒘𝒕 𝒔𝒐𝒍𝒖𝒕𝒆 𝒔𝒂𝒎𝒑𝒍𝒆 (𝒈) 𝒈𝒔𝒂𝒎𝒑𝒍𝒆
lowering, etc. A one-molal solution contains
one mole per 1000g of solvent. Trace concentrations are usually given in smaller units, such
as parts per thousand (ppt, ‰), parts per million (ppm), or
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝑴𝒐𝒍𝒂𝒍𝒊𝒕𝒚 = parts per billion (ppb).
𝒌𝒈 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆

• Normality (N)

A one-normal solution contains 1 equivalent per

liter

Equivalent
– represents the mass of a material
providing Avogadro’s number of
reacting units (proton – for acids and
bases or electron for redox reactions)

Equivalent weight

– - formula weight divided by reacting

units

𝒈𝒓𝒂𝒎𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝑵𝒐𝒓𝒎𝒂𝒍𝒊𝒕𝒚 =
𝑳 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒙 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒘𝒆𝒊𝒈𝒉𝒕

𝑵𝒐𝒓𝒎𝒂𝒍𝒊𝒕𝒚 = 𝑴 𝒙 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔

• Density-𝝆
• Dilution
𝒎𝒂𝒔𝒔 𝒌𝒈 𝒔𝒍𝒖𝒈𝒔
𝝆= = =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒎𝟑 𝒇𝒕𝟑 We often must prepare dilute solutions from more
concentrated stock solutions.

𝒄𝟏 𝒗𝟏= 𝒄𝟐 𝒗𝟐
• Specific Weight, 𝜸
Weight per unit volume of a substance STATISTICS AND DATA HANDLING IN ANALYTICAL
CHEMISTRY
𝒘𝒆𝒊𝒈𝒉𝒕 𝑵 𝒍𝒃
𝜸= = 𝒑𝒈 = 𝟑 = 𝟑
𝒗𝒐𝒍𝒖𝒎𝒆 𝒎 𝒇𝒕

Errors
• Specific Gravity (Relative Density) Two main classes of errors can affect the accuracy or
precision of a measured quantity: Determinate and
Ratio of the densities of two substances
Indeterminate errors
𝒑𝒔𝒖𝒃𝒔
𝑺𝑮 = • Determinate errors
𝑷𝒓𝒆𝒇
1. determinable and that presumably can
either be avoided or corrected

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Reviewer by: Jhecee Meir Tango BsCHE-1A

 2. nonrandom and occur when something is
intrinsically wrong in the measurement
3. causes the mean of a data set to differ from
the accepted value
• Systematic errors – measurable determinate errors
1. Instrumental errors – faulty equipment
2. Operative errors – personal errors
3. Errors of the method – some sources: side
reactions, incomplete reactions, impurities in
reagents, etc.
• Indeterminate errors
1. random, accidental; represent the experimental
uncertainty that occurs in any measurement
2. can arise from factors such as fluctuations in the
environmental conditions, or limitations in the
measurement apparatus
3. causes the data to be scattered more or less
symmetrically around a mean value
• Gross errors
1. lead to outliers (differ significantly from other
values)
2. occur infrequently and often result from an
experimental blunder
Accuracy and Precision
Accuracy – degree of agreement between the measured
value and the accepted true value
*Absolute True Value – exact, perfect value of the quantity
being measured, devoid of any error or uncertainty
*Accepted True Value – value that is generally agreed upon
by the scientific community as the most accurate
representation of a particular measurement
Precision - degree of agreement between replicate
measurements of the same quantity;
repeatability of a result Analytical chemists strive for
repeatable results to assure the highest possible accuracy.
Good precision does not guarantee accuracy!
Characterizing Experimental Errors
Accuracy is usually expressed as either an absolute error
𝑬 = 𝒙−𝝁
Mean error
𝑬 =→−𝝁
𝑿
or percent relative error
Reviewer by: Jhecee Meir Tango BsCHE-1A
→−𝝁
𝑿
𝑬𝑹 = 𝒙 𝟏𝟎𝟎
𝝁
where 𝜇is the expected (true value) and x" is the mean of
the measured values
Characterizing Experimental Errors
Precision may be expressed as the range, standard
deviation, or the variance
Range-Difference between the largest and smallest sample
values
Variance, s2
- preferred measure of variation when the mean is used as
the measure of center
-measures variation by indicating how far, on average, the
observations are from the mean
∑(𝑋𝑖 − 𝑋)2
𝑠2 =
𝑛−1
Standard Deviation, s
-positive square root of the sample variance
∑(𝑋𝑖 − 𝑋)2
𝑠=√
𝑛−1
Significant Figures
Significant figures are a reflection of a measurement’s
uncertainty.
Why recording a measurement to the correct number of
significant figures is important:
• it tells others about how precisely you made your
measurement
• they guide us in reporting the result of an analysis
Significant Figures: General Rules
1. All nonzero digits are significant.
2. But zeros must be considered on a case by case
basis. There are three types of zeros.
o Leading zeros – are not counted as significant
figures Example: 0.0034 – 2 s.f.
o Trailing zeros - Trailing zeros that follow a
decimal point are significant Example: 5800 – 2
s.f.
o Captive zeros – a zero between two nonzero
digits and is significant Example: 73.04 – 4 s.f.
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 3. Mathematical operations involving addition and
subtraction are carried out to the last digit that is
significant for all numbers included in the
calculation
4. When multiplying and dividing, the general rule
is that the answer contains the same number of
significant figures as that number in the
calculation having the fewest significant figures.

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Reviewer by: Jhecee Meir Tango BsCHE-1A