Analytical Chemistry

Qualitative and Quantitative

Analysis
 CHARACTERIZATION

Qualitative Analysis
- The identification of one or more chemical species present
in a sample

Quantitative Analysis
- The determination of the exact amount of a chemical species
present in a sample

Chemical Species
- Could be an element, ion or compound (organic or inorganic)
 CHARACTERIZATION

Bulk Analysis
- Characterization of the entire sample
Example: determination of the elemental composition of a mixture
(alloys)

Surface Analysis
- Characterization of the surface of a sample
Example: finding the thickness of a thin layer on the surface
of a solid material

- Characterization may also include Structural Analysis and

measurement of physical properties of materials
 THE ANALYTICAL APPROACH

Analyte
- A substance to be measured in a given sample

Matrix
- Everything else in the sample

Interferences
- Other compounds in the sample matrix that interfere
with the measurement of the analyte
 THE ANALYTICAL APPROACH
Homogeneous Sample
- Same chemical composition throughout
(sugar water, juice with no pulp, alcoholic beverages)

Heterogeneous Sample
- Composition varies from region to region within the sample
(pudding with raisins, granola bars with peanuts)

- Differences in composition may be visible or invisible to

the human eye (most real samples are invisible)

- Variation of composition may be random or segregated

 THE ANALYTICAL APPROACH
General Steps in Chemical Analysis

1. Formulating the question or defining the problem

- To be answered through chemical measurements

2. Designing the analytical method (selecting techniques)

- Find appropriate analytical procedures

3. Sampling and sample storage

- Select representative material to be analyzed

4. Sample preparation
- Convert representative material into a suitable form for analysis
THE ANALYTICAL APPROACH
General Steps in Chemical Analysis

5. Analysis (performing the measurement)

- Measure the concentration of analyte in several
identical portions

6. Assessing the data

7. Method validation

8. Documentation
 DEFINING THE PROBLEM

Qualitative Analysis

- Provides information about what is present in the sample

- If quantitative analysis is required, qualitative analysis

is usually done first

- Capabilities and limitations of analysis must be

well understood
 DEFINING THE PROBLEM

Qualitative Analysis

Qualitative Elemental Analysis

- Used to identify elements present in a material
- Can provide empirical formula of organic compounds
(X-Ray Fluorescence, AAS)

Qualitative Molecular Analysis

- Used to identify molecules present in a material
- Can be used to obtain molecular formula
- Can be used to distinguish between isomers
(NMR, IR, MS)
Title: Choline Chloride Sat Dec 10 10:02:45 2016 (GMT+07:00)

1653.81
2362.24

1241.44
90

1141.13
3004.49

1273.91
1412.68

423.00
80

1480.561459.31

1348.38

864.29

449.49
1376.10
% Transm ittance

1011.33

892.04
70

464.49
629.42
3217.22

1056.63

528.31
1083.40
60

951.24
50

40

30

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)
Spectrum:
Collection time: Sat Dec 10 10:01:08 2016 (GMT+07:00) Choline Chloride
Sat Dec 10 10:02:30 2016 (GMT+07:00) Region: 3495.26-455.13
FIND PEAKS: Search type: Correlation
Spectrum: Choline Chloride
Region: 4000.00 400.00 Hit List:
Absolute threshold:
Sensitivity: 50
97.346
Index Match Compound name Library
Peak list: 2447 71.79 Choline chloride, 99+% HR Aldrich FT-IR Collection Edition II
Position: 423.00 Intensity: 83.727
Position: 449.49 Intensity: 77.316 2450 36.89 Choline bicarbonate, 75 wt. % solution i HR Aldrich FT-IR Collection Edition II
Position: 464.49 Intensity: 70.066 n water
Position: 528.31 Intensity: 69.647
Position: 629.42 Intensity: 69.668 14327 33.72 4-Bromo-2,3,5,6-tetrafluoropyridine, 98% HR Aldrich FT-IR Collection Edition II
Position:
Position:
864.29
892.04
Intensity:
Intensity:
77.270
71.309
3316 33.69 Tetramethylammonium formate, 25 wt. % so HR Aldrich FT-IR Collection Edition II
Position: 951.24 Intensity: 57.462 lution in water, 99.99+%
Position: 1011.33 Intensity: 72.771
Position: 1056.63 Intensity: 76.107 18276 32.47 Ammonium hydrogenphosphate, 98+%, A.C.S. HR Aldrich FT-IR Collection Edition II
Position: 1083.40 Intensity: 69.202 reagent
Position: 1141.13 Intensity: 86.359
Position: 1241.44 Intensity: 90.873 27 31.32 D-SPHINGOSINE FROM BOVINE BRAIN*S Sigma Biological Sample Library
Position:
Position:
1273.91
1348.38
Intensity:
Intensity:
89.677
78.523
1503 31.19 2,5-Dihydrofuran, 97% HR Aldrich FT-IR Collection Edition II
Position: 1376.10 Intensity: 88.970 5640 30.73 Dichloromalononitrile, 95% HR Aldrich FT-IR Collection Edition II
Position: 1412.68 Intensity: 84.362
Position: 1459.31 Intensity: 83.062 16504 30.52 Dichloromethane-d2, 99.95 atom % D HR Aldrich FT-IR Collection Edition II
Position: 1480.56 Intensity: 68.687 438 29.90 Ammonium phosphate dibasic HR Nicolet Sampler Library
Position: 1653.81 Intensity: 95.426
Position: 2362.24 Intensity: 95.244
Position: 3004.49 Intensity: 85.878
Position: 3217.22 Intensity: 68.986
 DEFINING THE PROBLEM
Quantitative Analysis

- The determination of the amount of analyte in a given sample

- Often expressed in terms of concentrations

Concentration
- The quantity of analyte in a given volume or mass of sample

Molarity = moles/liters, ppm = µg/g sample

ppb = ng/g sample, ppt = pg/g sample
Percent by mass [%(m/m)], Percent by volume [%(v/v)]
 DEFINING THE PROBLEM
Quantitative Analysis

- Early methods include volumetric, gravimetric, and

combustion analysis

- Automated and extremely sensitive methods are being

used today (GC, IR, HPLC, CE, XRD)

- Require micron amounts and a few minutes

 SAMPLING
- The most important step is the collection of the sample of the
material to be analyzed

- Sample should be representative of the material

- Sample should be properly taken to provide reliable

characterization of the material

- Sufficient amount must be taken for all analysis

Representative Sample
- Reflects the true value and distribution of analyte in the
original material
 SAMPLING
- Care must be taken since collection tools and storage
containers can contaminate samples

- Make room for multiple test portions of sample for replicate

analysis or analysis by more than one technique

Samples may undergo

- grinding
- chopping
- milling
- cutting
 SAMPLING
Gas Samples

- Generally considered homogeneous

- Samples are stirred before portions are taken for analysis

- Gas samples may be filtered if solid materials are present

Grab samples
- Samples taken at a single point in time

Composite Samples
- Samples taken over a period of time or from different locations
 SAMPLING
Gas Samples

Scrubbing
- Trapping an analyte out of the gas phase

Examples
- Passing air through activated charcoal to adsorb organic vapors
- Bubbling gas samples through a solution to absorb the analyte

Samples may be taken with

- Gas-tight syringes
- Ballons (volatile organic compounds may contaminate samples)
- Plastic bags (volatile organic compounds may contaminate
samples)
- Glass containers (may adsorb gas components)
 SAMPLING
Liquid Samples

- May be collected as grab samples or composite samples

- Adequate stirring is necessary to obtain representative sample

- Stirring may not be desired under certain conditions

(analysis of oily layer on water)

- Undesired solid materials are removed by filtration

or centrifugation

- Layers of immiscible liquids may be separated with the

separatory funnel
 SAMPLING

Solid Samples

- The most difficult to sample since least homogeneous

compared to gases and liquids

- Large amounts are difficult to stir

- Must undergo size reduction (milling, drilling, crushing, etc.)

to homogenize sample

- Adsorbed water is often removed by oven drying

 SAMPLING
Sample Storage

- Samples are stored if cannot be analyzed immediately

- Sample composition can be changed by interaction with

container material, light, or air

- Appropriate storage container and conditions must be chosen

- Organic components must not be stored in plastic containers

due to leaching

- Glass containers may adsorb or release trace levels of ionic species

 SAMPLING
Sample Storage

- Appropriate cleaning of containers is necessary

- Containers for organic samples are washed in solvent

- Containers for metal samples are soaked in acid

and deionized water

- Containers must be first filled with inert gas to displace air

- Biological samples are usually kept in freezers

- Samples that interact with light are stored in the dark

 ACCURACY AND PRECISION
- Accuracy is how close a measurement is to the true
(accepted) value

- True value is evaluated by analyzing known standard samples

- Precision is how close replicate measurements on the

same sample are to each other

- Precision is required for accuracy but does not

guarantee accuracy

- Results should be accurate and precise

(reproducible, reliable, truly representative of sample)
 ERRORS
- Two principal types of errors

- Determinate (systematic) and indeterminate (random)

Determinate (Systematic) Errors

- Caused by faults in procedure or instrument
- Fault can be found out and corrected
- Results in good precision but poor accuracy

May be
- constant (incorrect calibration of pH meter or mass balance)
- variable (change in volume due to temperature changes)
- additive or multiplicative
 ERRORS
- Two principal types of errors

- Determinate (systematic) and indeterminate (random)

Examples of Determinate (Systematic) Errors

- Uncalibrated or improperly calibrated mass balances
- Improperly calibrated volumetric flasks and pipettes
- Analyst error (misreading or inexperience)
- Incorrect technique
- Malfunctioning instrument (voltage fluctuations, alignment, etc)
- Contaminated or impure or decomposed reagents
- Interferences
 ERRORS
- Two principal types of errors

- Determinate (systematic) and indeterminate (random)

To Identify Determinate (Systematic) Errors

- Use of standard methods with known accuracy and precision
to analyze samples

- Run several analysis of a reference analyte whose concentration

is known and accepted

- Run Standard Operating Procedures (SOPs)

 ERRORS
- Two principal types of errors

- Determinate (systematic) and indeterminate (random)

Indeterminate (Random) Errors

- Sources cannot be identified, avoided, or corrected
- Not constant (biased)

Examples
- Limitations of reading mass balances
- Electrical noise in instruments
 ERRORS
- Random errors are always associated with measurements

- No conclusion can be drawn with complete certainty

- Scientists use statistics to accept conclusions that have high

probability of being correct and to reject conclusions that have
low probability of being correct

- Random errors follow random distribution and analyzed

using laws of probability

- Statistics deals with only random errors

- Systematic errors should be detected and eliminated

 S?
T I ON
Q UES
Y
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11/11/2021
Contact :
LinkedIn : Helda Niawanti Source : Clayton University, Analytical Chemistry
Email : heldaniawanti@gmail.com ppt
Video : Techinstro & FuseSchool YT Channel 27