INSTRUMENTAL ANALYSIS

DEALS WITH METHODS FOR DETERMINING THE CHEMICAL COMPOSITION OF SAMPLES MATTER
which exploit phenomenon other than those used for classical analytical chemistry, e.g physical properties
as conductivity, electrode potential, light absorption or emission, mass-to-charge ratio etc

QUALITATIVE METHODS QUANTITATIVE METHODS

Information about the identity of Numerical information as to the relative

atomic or molecular species or the amount of one or more components
functional groups in the sample
 Communication device
between the system under study and the investigator

An instrument for chemical analysis converts information about the physical or chemical characteristics of the analyte
to information that can be manipulated and interpreted by a human

Stimulus Response

Energy source System under study Analytical information

Characteristic Properties Instrumental method
Absorption of radiation Spectrophotometry and photometry (X-ray, UV, vis, IR); photoacoustic
spectroscopy; nuclear magnetic resonance; electron spin resonance
Emission of radiation Emission spectroscopy (X-ray, UV, vis, electron); fluorescence
phosphorescence, luminescence (X-ray, UV, vis)
Scattering of radiation Turbidimetry, Raman spectroscopy
Refraction of radiation Refractrometry, interferometry
Diffraction of radiation X ray and electron diffraction methods
Rotation of radiation Polarimetry, circular dichroism
Electrical potential Potentiometry
Electrical charge Coulometry
Electrical current Amperometry
Electrical resistance Conductometry
Mass Gravimetry
Mass-to-charge ratio Mass spectrometry
Thermal characteristics Thermal gravimetry, differential scanning calorimetry, differential thermal
analysis; thermal conductometric methods
 Chemistry
Biochemistry
Inorganic chemistry
Biology Organic chemistry
Physical Chemistry Physics
Botany
Astrophysics
Genetics
Astronomy
Microbiology
Biophysics
Molecular biology

Geology
Engineering
Geophysics
Civil
Geochemistry
Chemical Electrical
Paleobiology
Mechanical
Paleontology

Analytical
methods
Environmental Medicine
Sciences Clinical Chemistry
Ecology Medicinal Chemistry
Meteorology Pharmacology
Oceanography Toxicology

Agricolture
Material Science
Agronomy
Metallurgy
Animal Science
Polymers
Food Science
Social Sciences Solid State
Soil Science
Archeology
Anthropology
Forensic
 A famous example of instrumental analysis: chemical composition of Mars

https://mars.nasa.gov/mars-exploration/missions/pathfinder/
 FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

Carry out
chemical
dissolution

No

Is Yes Yes
Measura
sample ble Estimate
Acquire Process Issoluble
sample Eliminate Measure Calculate
Select method property realiability of
sample sample soluble?
? ? interferences property X results
results

No

Change
chemical
form
 FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

Carry out
chemical
dissolution

No

Is Yes Yes
Measura
sample ble Estimate
Acquire Process Issoluble
sample Eliminate Measure Calculate
Select method property realiability of
sample sample soluble?
? ? interferences property X results
results

ü It requires experience and intuition No

ü Which level of accuracy required?

ü Usually compromise between accuracy, time and money chemical
Change

(the higher the accuracy, the longer the time the more expensive
form the analysis)
ü Number of samples
ü Complexity of the sample
 FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

Carry out
chemical
dissolution

No

Is Yes Yes
Measura
sample ble Estimate
Acquire Process Issoluble
sample Eliminate Measure Calculate
Select method property realiability of
sample sample soluble?
? ? interferences property X results
results

No whose composition accurately represents the bulk

Process of collecting a small mass of materials
ü Need of representative sample
ü Homogeneous vs heterogeneous sampleschemical Change

ü Complex sample? form

ü Sealed vial for gaseous sample or liquid containing gas

ü Liquid in closed vial to avoid evaporation, i.e. change of concentration
ü Replicates: a number of sample speciments with known mass/volume to minimize the error,
increase reliability and accuracy of the analysis; results are averaged
 Simple FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

Carry out
chemical
dissolution

No

Is Yes Yes
sample Estimate
Select Acquire Process Is sample Measurabl Eliminate Measure Calculate
soluble e realiability of
method sample sample soluble? property? interferences property X results
? results

This step sometimes is required,No sometimes can be avoided.

It depends on the complexity of the sample, on the physical state of the matter to be analysed
ü For solid samples: grounded,Changemixed, dried
chemical
ü An important question: is sampleform soluble?
ü If the method requires a liquid sample, a chemical dissolution has to be carried out,
including change of the environmental condition (e.g. increasing temperature), use of acids,
chemical reaction to a soluble product (e.g. oxidation, reduction..). In this last case the
reaction has to be selective and quantitative. Ex. Mn +O2 MnO4 (coloured solution)
ü Examples of insoluble samples include metals, silicate minerals, high-molecular weight
polymers, specimens of animal tissue
 FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

One of the properties mentioned in slide 3 is measured. If

the selected property is measurable, an important step is
determining whether substances other than the analyte
Carry out
chemical can interfere with the measurement
dissolution
Species other than the analyte that affect the final
No
measurement are called interferences or interferents.
Is Yes Yes
sample Measurab Estimate
Acquire Process Issoluble
sample Eliminate Measure Calculate
Select method le realiability of
sample sample soluble?
? interferences property X results
property? results

No

The measured property X of the analyte must vary in a known and reproducible way with the concentration cA.
Ideally, the measured property is directly proportional to the concentration. That is:
Change
chemical
form

cA=kX

where k is a proportionality constant. With few exceptions, analytical methods require the empirical determination of k
with chemical standard for which cA is known
CALIBRATION: the process of determining k
 FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

Carry out
chemical
dissolution

No

Is Yes Yes
Measura
sample ble Estimate
Acquire Process Issoluble
sample Eliminate Measure Calculate
Select method property realiability of
sample sample soluble?
? ? interferences property X results
results

No
Data are usually computed by software,
Change
which considers the raw experimental
chemical
form
data collected in the measurement step,
the characteristic of the measurement
instruments and the specific instrumental
setting
 FLOW DIAGRAM OF A QUANTITATIVE ANALYSIS

Carry out
chemical
dissolution

No

Is Yes Yes
Measura
sample ble Estimate
Acquire Process Issoluble
sample Eliminate Measure Calculate
Select method property realiability of
sample sample soluble?
? ? interferences property X results
results

No
The results obtained must be carefully
analysed to:
Change
chemical Estimate the measurement error
form
Verify the absence of instrumental artefacts
Check if the data lie in the range of validity
of the calibration
 Use of analytical chemistry to solve a problem in toxicology
A CASE STUDY: DEER KILL

Quantitative analysis was used to determine the agent that caused deaths in a population
of deer inhabìting a wildlife preserve of a national recreational area in Kentucky.

The Problem
The incident began when a park ranger found a dead deer near a pond in the land
between the Lakes National Recreation Area in western Kentucky. The ranger enlisted the
help of a chemist to find the cause of death. The ranger and the chemist investigated the
site where the badly decomposed carcass of the deer had been found.
Because of the advanced state of decomposition. no fresh organ tissue samples could be
gathered. A few days after the original inquiry. the ranger found two more dead deer
near the same location. The investigators then conducted a careful examination of
the surrounding area to find clues to the cause of death.

The CLUE: the investigators noticed that grass surrounding was wilted and discolored.
They speculated that a herbicide might have been used on the grass.
 QUESTION: Which herbicides are widely used in US?

Sodium salt of methanearsenic acid

(very soluble in water)

The herbicidal activity of disodiuym methanearsenate is due to its reactivity with the sulfhydryl (S-H) in the
aminoacid cysteine. When cysteine in plant enzymes reacts with arsenical compounds, the enzyme function is
inhibited and the plant eventually dies. Unfortunately; similar chemical effects occur in animals as well.

SAMPLES: 1) discolored grass

2) deer

SELECT A METHOD
Quantitative determination of As: distillation of the compound as arsine, and its colorimetric measurements