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ADIBAH BINTI MOHD

NOOR

CHAPTER 1:
INTRODUCTION OF ANALYTICAL CHEMISTRY
SYLLABUS CONTENT
 Types and steps in analysis.
 Review the terms: moles, molarity and concentration.
 Other expressions of concentration: % (w/w), % (w/v),
% (v/v), ppm, ppt, ppb.
 Calculations involving different expressions of concentrations.
LEARNING OUTCOME

 In this chapter, student should be able to:

 Differentiate between qualitative & quantitative analysis.


 Explain the steps involve in quantitative analysis.
 Calculate the concentration of solution.
 Explain the preparation of solution.
WHAT IS
ANALYTICAL CHEMISTRY?
“Analytical Chemistry is what analytical
chemists do.”
- C. N. Reilley

• Chemical analysis is more than just detecting or


determining the general composition or a specific
component of a sample.
• It is the resolution or interpretation of a given problem.
WHAT IS
ANALYTICAL CHEMISTRY?

• Chemical analysis:
 Determination of the chemical composition or chemical
make up as well as the quantity of each composition
presence in a sample.

Examples:
o The chemical analysis of a blood sample involves the determination of
its iron content, its alcohol content, or perhaps its drug content and
how much each of the composition presence in the blood sample.

o The chemical analysis of a water sample involves the determination of


its mineral content, its pollutant content, and its dissolved oxygen
content and the percentage of each constituents.
IMPORTANCE OF ANALYTICAL CHEMISTRY

 Provide methods and tools to collect data to solve problems in


FIELDS OF SCIENCE such as:
 Industry, Medicine, Environment, Chemistry, Biology,
Agriculture, Materials Science, Archeology, Forensic Science,
Geology, Physics, Engineering and more.
 In analysis, QUALITATIVE & QUANTITATIVE
information are required.
1. TYPE & STEPS IN ANALYSIS
DISCIPLINE OF ANALYTICAL CHEMISTRY
ANALYTICAL
CHEMISTRY

QUALITATIVE QUANTITATIVE
ANALYSIS ANALYSIS
Analysis to identify the Analysis to determine
constituents (elements, the relative amounts of
atoms, ions, compounds) the constituents
present in a sample. presence in a sample.

WHAT IT IS? HOW


MUCH?
QUALITATIVE vs QUANTITATIVE ANALYTE:
chemical
substances in a
sample that are
being identified

QUALITATIVE QUANTITATIVE
To determine the PRESENCE or ABSENCE of a To determine the EXACT AMOUNT of that
substance in a sample substance/analyte in a sample
CHEMICAL IDENTITY of the substance of the QUANTITY of the species in a sample.
sample. (Concentration/level/percentage/mass/relative
(Type of species/analyte/atom/ion/ abundance)
molecule/functional group present)

Eg: Eg:
1. The presence of copper ion detected 1. The concentrations of oxygen in blood
when flame colour is green samples is equal to 3 mL O2/liter blood.
2. Identifying anions and cations in 2. The percentage by mass of silver is 42.88% in
aqueous solution ore.

Achieved by: Achieved by:


• Color changes, distillation, extraction • Adsorption of light, density, chemical reactions,
• Gravimetry: precipitation precipitation
• Chromatography: separation • Volumetric: Titration
METHOD OF CHEMICAL ANALYSIS

 To estimate the concentration of an analyte may require both measurement of


the mass or volume of the sample and some physical quantity that is related
to the concentration of the element or compound.

 This quantity can be classified as:


 Gravimetric [mass of a precipitate]
 Volumetric [volume of a titration]
 Electroanalytical [voltage, current, amount of charge]
 Spectroscopic [absorbance, fluorescence, emission]
 Miscellaneous [radioactivity, reaction rate, refractive index]
EXERCISES
State the types of analysis: qualitative analysis, quantitative
analysis or both.

a. To determine and compare the percentage yield of fish oil in siakap


and tilapia fish

b. To determine the presence of ascorbic acid in canned fruit juices

c. To determine the amount of potassium content in varieties of local


durians.

d. A hazardous-waste disposal site is believed to


be leaking contaminants into the local groundwater.

a. A quick way is needed to find the level of blood


pressure among men above 60 years old that can categorized
as high BP.

f. A reliable method is needed by airport security for detecting the


presence of explosive materials in luggage.
STEPS IN ANALYTICAL CHEMISTRY
Defining the problem

Selecting the method

Obtain a representative sample

Prepare the sample for analysis

Eliminating interferences

Performing the measurements

Calculating the results and reporting the data


STEP 1 DEFINING THE PROBLEM
 To obtain required information within a period of
time

 Know what information is needed, by whom, what


purpose & what type of sample is to be analyzed.
 Depend on equipment available, cost,
time involved.
STEP 2 SELECT A METHOD

 Know origin of the sample.


 Factors to select a method:
• Sample type
• Size of sample
• Level accuracy
• Sample preparation needed
• Transportation or storage of sample

 Complexity of sample & no of components


in sample influence the choice of method applied.
STEP 3 OBTAIN A REPRESENTATIVE SAMPLE

 Representative sample: A small quantity/portion of materials


that represent the whole sample of population.

 Sample (Solid/Liquid/Gas) may be homogeneous or heterogeneous.


 The suitable sampling method differ from one substance to another
depending on homogeneity.

 Gross sample:
• consist several portions of tested material.
• must be reduced in size to gain laboratory sample.

 Laboratory sample:
• small portion, crushing or sieving to form
homogeneous or uniform powder for analysis.
• the analysis sample that actually analyzed.
STEP 4 PREPARE THE SAMPLE FOR ANALYSIS

 Preparing laboratory samples


 SOLIDS : grinding, mixing, storage to avoid changes (water content, oxidation).
 LIQUIDS : solvent & analyte evaporation, storage to minimize chemical changes
(refrigeration, freezing, deoxygenate, dark).

 Preparing and storage the solutions


 Physical & chemical changes can occur
 know suitable solvent used
(acid, base, oxidant, reductant, organic solvent)
STEP 5 ELIMINATING INTERFERENCES

 Perform necessary chemical separation to remove


interference

 Impurities may decrease the spectroscopic signal used


to calculate the concentration.
 Separation step include precipitation, extraction,
chromatography, distillation.

INTERFERENCE
Species other than analyte
that can cause ERROR & affect
the final measurement
STEP 6 PERFORMING THE MEASUREMENTS

 Replicates samples
 Improve the quality of the results & provide a measure
reliability.

 Analysis
 Incorporates the measurement of the concentration of the
analyte in replicates and comparing with standards.

 Gravimetric analysis
 based on MEASUREMENT OF MASS (precipitation)

 Volumetric analysis
 based on MEASUREMENT OF VOLUME (titration)
STEP 6 PERFORMING THE MEASUREMENTS

 Instrumental techniques

 More selective and sensitive than


volumetric & gravimetric.
 Instrumentation must be
calibrate.
 Calibration is accomplished by preparing
a series of standard solutions of the
analyte at known concentrations.
 Calibration curve – instrument response
(function of concentration).
CALCULATING THE RESULTS
STEP 7
AND REPORTING THE DATA

 Calculate & Evaluate the results

 Toestimate whether results are reliable or not:

1. PRECISION : Estimate using the standard deviation.


(based on replicate measurements)

2. ACCURACY : Evaluate by refer to standard materials

Precision and accuracy is very important in analytical


chemistry and referred as quality control
or quality assurance.
2. MOLES, MOLARITY, CONCENTRATION

UNITS FOR QUANTITY & CONCENTRATIONS

 Mole and milimoles


 Concentrations & its Definition
 Density and Specific Gravity
 Molarity, Molality
 Percentage Concentration:
 % w/w, % w/v, % v/v
 ppm, ppb, ppt
2. MOLES, MOLARITY, CONCENTRATION
UNITS FOR QUANTITY & CONCENTRATIONS

MOLE
• The mole (mole) is the SI unit for the amount of a chemical
species.
• One mole (mol) is the amount of a substance that contains as
many entities (atoms, molecules or ions) as there are in 12.0 g
of C12 atoms.
• The mass in grams of 1 mole of a substance
is called its molar mass.
2. MOLES, MOLARITY, CONCENTRATION
RELATIONSHIP BETWEEN MOLE & NUMBER OF
ENTITIES

 1 mole of atoms/molecules/ions of any element will MOLE


contain Avogadro’s number of atoms/molecules/ions or
6.022 x 1023 atoms/molecules/ions of that element.

For example:
 1 mol of Mg atom contain 6.022 x 1023 Mg atoms.
 1 mol of H2O molecule contain 6.022 x 1023 H2O
molecules.
 1 mol of Na+ ions contain 6.022 x 1023 Na+ ions
EXERCISES

Number of entities = number of moles x 6.022 x 1023

1. Calculate the number of atoms in 1 mol of aluminium atoms.


(6.02 x 1023)
2. Calculate the number of atoms in 0.5 mol of aluminium atoms.
(3.02 x 1023)
3. If a container has 12.0 x 1023 atoms of magnesium, determine
number of moles of magnesium atoms. (2.0 moles)

4. How many molecules of CO2 are found in 3.5 moles of CO2?


(2.1 x 1024)
5. How many Cl- ions are present in 0.25 moles of CaCl2?
(3.0 x 1023)
2. MOLES, MOLARITY, CONCENTRATION
UNITS FOR QUANTITY & CONCENTRATIONS

MOLE & MILIMOLE

1 g= 1000 mg
1 mol = 1000 mmol
1 L = 1000 mL
EXAMPLE
EXAMPLE
EXAMPLE
FORMULA
EXERCISES
RELATIONSHIP BETWEEN MOLE & NUMBER OF ENTITIES
1. Calculate the number of moles for 3.4 g of carbon atoms.
(0.28 moles)
2. Find the mass of 0.30 moles of CH4 (4.8 g)
3. Calculate no of moles of Cl- is present in 0.34 moles of CaCl2
(0.68 moles)
4. Find the mass of H in 2.5 moles of H2O? (5.0 g)
5. Find the mass of O in 3.0 moles of CO2? (96.0 g)
2. MOLES, MOLARITY, CONCENTRATION

CONCENTRATION
WATER is considered a
universal solvent for
most solutions

Concentration is the amount of solute in a given volume of solution.

 SOLUTION: A homogenous mixture of two or more substances,


consisting of solvent and solute.

 SOLUTE: The substance present in a smaller proportion of the


solution. It can be solid, liquid or gas.

 SOLVENT: A substance that generally a liquid present in the larger


proportion of the solution.
2. MOLES, MOLARITY, CONCENTRATION

DENSITY & SPECIFIC GRAVITY OF SOLUTION


 Density of a substance is the mass per unit volume.
 In SI unit, density is expressed in unit of kg per liter, (kg/L) or in metric
system the unit use is gram per milliliter, (g/mL).
 Density of water = 1 g/mL
 Specific gravity is the ratio of the mass of an equal volume of water at
4oC.
 Specific gravity is dimensionless.
2. MOLES, MOLARITY, CONCENTRATION

MOLARITY OR MOLAR CONCENTRATION


 Molarity : no of moles of the solute in 1 L (dm3) of solution
 Molar mass (atomic mass) : the mass of 1 mole of a
substance in unit gram. (Unit for molar mass : g/mol)
 Unit for Molarity (M): (mol/L), (mmol/mL).
M = no of mol of solute (mol)
volume of solution (L)
or
M = no of mmol of solute (mmol)
volume of solution (mL)
EXAMPLE
1. Calculate the molar concentration of ethanol in aqueous solution that
contains 2.30 g C2H5OH (46.07 g/mol) in 3.50 L of solution.

No of mole C2H5OH = 2.30 g = 0.4992 mol


46.07 g/mol

Molarity = 0.04992 mol = 0.0143 M


3.5 L
EXAMPLE
Try this!!
2. Sea water contains roughly 28.0 g of NaCl per liter.
What is the molarity of sodium chloride in sea water?

No of mole NaCl = 28.0 g = 0.4791 mol


58.44 g/mol

Molarity = 0.4791 mol = 0.4791 M


1L
EXAMPLE

3. What is the molarity of 5.30 g of Na2CO3 dissolved in


400.0 mL solution?

No of mole Na2CO3 = 5.30 g = 0.05 mol


106 g/mol

Molarity = 0.05 mol = 0.125 M


0.4 L

1 L = 1000 mL
Remember!! 1 dm3 = 1000 cm3
• convert volume
to L or dm3
2. MOLES, MOLARITY, CONCENTRATION

MOLALITY
 Number of moles of solute that dissolved in 1000 g of solvent, m
 Preferred expression of concentration involving colligative
properties such as (boiling point elevation, freezing point
depression, osmotic pressure)
 Unit for molality, m = (mol/kg)

FORMULA!!
m = no of mol of solute (mol)
1 kg of solvent (kg)
EXAMPLE

1. If you have 10.0 grams of Br2 and dissolve it in 1.00 L of cyclohexane,


what is the molality of the solution? The density of cyclohexane is 0.779
kg/L at room temperature.

Mol of Br2 = 10 g = 0.063 moles Br2


(159.8 g/mol)

Next, convert the volume of solvent to the weight of solvent using the
density
= 1.00 L x 0.779 kg/L = 0.779 kg

Now just divide the two to get the molality Molality, m


= 0.063 moles Br2 = 0.080 molal
0.779 kg cyclohexane
EXAMPLE
Try this!!
2. A sulfuric acid solution containing 571.4 g of H2SO4 per liter of solution
has a density of 1.329 g/cm3. Calculate the molality of H2SO4 in this
solution

No of mol H2SO4 = 571.4 g = 5.826 mol


(98.0768 g/mol)

Mass of solvent:
1 L of solution = 1000 mL = 1000 cm3
1.329 g/cm3 times 1000 cm3 = 1329 g (the mass of the entire solution)
1329 g - 571.4 g = 757.6 g = 0.7576 kg (the mass of water in the solution)

Molality, m = 5.826 mol / 0.7576 kg = 7.690 m


3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)

% CONCENTRATION

 Concentration can be described in term of % (percentage)


concentrations.

 % concentrations (% w/w, w/v, v/v),


 Number of parts in 100 parts
 eg. Gram of A in 100 grams of sample.

% of A = number of parts of A x 100 %


number of parts of sample
3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)

1. % WEIGHT/WEIGHT TO EXPRESS THE


CONCENTRATION OF
% (w/w) COMMERCIAL REAGENTS

 Percent weight in weight concentration which is weight in 100 g of sample.

 Weight percent (w/w) = weight of solute (g) x 100 %


weight of sample (g)
 Example: A nitric acid, HNO3 is sold as 70%
solution.
- It means that the reagent contains 70 g pure per
100 g solution.

 70 % w/w = 70 g pure HNO3 x 100 %


100 g solution
3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)

1. % WEIGHT/WEIGHT
% (w/w)

EXAMPLE
Calculate the molarity of the following acids.

a) 70 % (w/w) HClO4, density = 1.67 g/mL

70 g x 1.67 g x 1000 mL x 1.0 mol = 11.63 mol/L


100 g 1.0 mL 1.0 L 100.5 g

b) 96 % (w/w) H2SO4, density = 1.84 g/mL

96 g x 1.84 g x 1000 mL x 1.0 mol = 18.02 mol/L


100 g 1.0 mL 1.0 L 98.0 g
3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)

1. % WEIGHT/WEIGHT
% (w/w)
EXAMPLE
c) Briefly explain how to prepare the following solution in the laboratory. 500 mL of 2.0 M
H2SO4 from a commercial reagent at 90 % (w/w) purity and specific gravity of 1.84.

90 g x 1.84 g x 1000 mL x 1.0 mol = 16.9 mol/L


100 g 1.0 mL 1.0 L 98.0 g

Molarity H2SO4 = 16.9 M,


Find volume need to transfer from commercial reagent H2SO4

McVc = MdVd , Vc = 2.0 M (500 mL) = 59.2 mL


16.9 M

So, measure and transfer 59.2 mL from commercial reagent to 500 mL of volumetric flask.
Dilute with distilled water until calibration mark. Shake upside down.
3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)
2. % WEIGHT/VOLUME TO INDICATE THE

% (w/v) COMPOSITION OF DILUTE


AQUEOUS SOLUTION OF
SOLID REAGENTS

 Percent weight in volume concentration which is weight in 100 mL of


sample.
 Weight percent (w/v) = weight of solute (g) x 100 %
volume of sample (mL)

 Example: A 5 % aqueous silver nitrate refers,


AgNO3 to solution prepared by dissolving 5 g
of AgNO3 in sufficient water to give 100 mL
of solution.

 5 % w/v = 5 g AgNO3 x 100 %


100 mL solution
3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)

2. % WEIGHT/VOLUME
% (w/v)

EXAMPLE
1. Briefly explain how to prepare the following solutions ( 1.0 L, 10.50 % (w/v) aqueous
CH3CH2CH2OH.

% (w/v) = mass (g) x 100 , 10.5 % = mass (g) x 100,


volume (mL) 1000 mL

So mass CH3CH2CH2OH = 10.5 (1000 mL) = 105 g


100

Weigh 105 g of CH3CH2CH2OH, dissolve with small amount of distilled water, transfer to 1.0 L of
volumetric flask, dilute with distilled water to the calibration mark. Shake upside down.
3. EXPRESSION OF CONCENTRATION (PERCENTAGES %)

3. % VOLUME/VOLUME TO SPECIFY THE CONCENTRATION


OF A SOLUTION PREPARED BY

% (v/v) DILUTING A PURE LIQUID WITH


ANOTHER LIQUID

 Percent volume in volume concentration which is volume in 100 mL of


sample.
 Weight percent (w/v) = volume of solute (mL) x 100 %
volume of sample (mL)

 Example : A 5 % aqueous methanol solution


means 5 mL of methanol dissolve in enough
distilled water to make 100 mL solution.

 5 % v/v = 5 mL ethanol x 100 %


100 mL solution
3. ANOTHER EXPRESSION OF CONCENTRATION

4. ppt, ppm, ppb


(for SOLID & LIQUID)

 Part per thousand (ppt), part per million (ppm) and part per billion (ppb)
 For sample that contain smaller amount of component the concentration is
expressed in terms of ppt, ppm or ppb.

1. ppt = parts per thousand (103) :


Number of parts of a substance found in one thousands parts of a particular gas,
liquid or solid.

2. ppm = parts per million (106) :


Number parts of a substance present in one million parts of solvent (water)

3. ppb = parts per billion (109)


3. ANOTHER EXPRESSION OF CONCENTRATION

4. ppt, ppm, ppb


(for SOLID & LIQUID)

• ppb = parts per billion (109)


• pptr = part per trillion (1012)
• Eg : ppm(106)
If we use gram as the unit, 1 ppm means we have 1 g of substance in
1,000,000 g solvent.
3. ANOTHER EXPRESSION OF CONCENTRATION

4. ppt, ppm, ppb


(for SOLID & LIQUID)
Expression (unit) of concentration ppt/ppm/ppb in terms of percentage of w/w,
w/v & v/v

w/w v/v w/v FACTOR


g/g x 103 mL/mL x 103 g/mL x 103
103
ppt mg/g mL/L mg/mL
g/kg µL/mL g/L
g/g x 106 mL/mL x 106 g/mL x 106
106
ppm mg/kg µL/L mg/L
µg/g nL/mL µg/mL
g/g x 109 g/mL x 109
mL/mL x 109
ppb µg/kg µg/L 109
nL/L
ng/g ng/ml
3. ANOTHER EXPRESSION OF CONCENTRATION

4. ppt, ppm, ppb


(for SOLID & LIQUID)

EXAMPLE
1. Calculate w/v in ppm of sodium in a solution containing
2.500mg of Na+ in 500 mL of solution.

ppm (w/v) = mg of analyte = 2.500 mg = 5 ppm


L of solution 0.5 L

Or

ppm (w/v) = g of analyte x 106


ml of solution
= 2.5 x 10-3g x 106
500mL
= 5 ppm
EXAMPLE
2. An analysis for cadmium in water give a value of 1.20 ppb
(w/v). What mass of cadmium is contained in 1.00 L water?

ppb = g/mL x 109

? g x 109 = 1.20
103 mL
? g = 1.2 x 103
109
= 1.2 x 10-6 g
= 1.2 µg
EXAMPLE
3. Determine the ppm of ferrous ion, Fe2+, in a solution known
to be 1.2 × 10-6 M Fe3(PO4)2.8H2O
(RMM=501.61) Answer: 0.6ppm
EXAMPLE
4. Describe the preparation of 1 L 0.1 M HCl from
concentration HCl 37% w/w and with density 1.18 g/mL
EXAMPLE
1. Molarity (concentrated) = percentage (%) x (density/RMM) X 1000
2. M1V1 (concentrated) = M2V2 (diluted)

Using 2 formula:
EXAMPLE
EXAMPLE
5. Describe the preparation of a 250 mL 50 ppm solution
of AgNO3 from solidchemical.
EXAMPLE
6. Describe the preparation of 0.5 L 50 ppm of Cl- from solid KCl.
EXAMPLE
7. Calculate mass in gram of Ba(NO3)2 is needed to prepare a 50 mL
solution containing 100 ppm NO3-?
EXAMPLE
EXAMPLE
EXAMPLE
EXAMPLE
How many milliliters of concentrated sulfuric acid, 94.0% (g/100 g
solution), density 1.831 g/cm3, are required to prepare 1 L of 0.100
M solution?
Extra note!
 Preparation of solution: Describe to prepare the solution - include 2 parts
1) calculation and
2) sentence to prepare the solution (in detail)

 From raw material :


1) Solid Standard Reagent • Transfer to
volumetric flask (mL)
• Dilute until
calibration mark.
• Shake upside down
weigh mass (g) dissolve with small amount
of solid reagent of distilled water

2) Liquid Concentrated Acid or Base

• Transfer to volumetric
flask (mL)
• Measure mL • Dilute until calibration
mark.
• Shake upside down
EXERCISES
1. Define:
a) Parts per million
b) Molality
c) Molarity
d) Percentage

2. Calculate the number of mole in the following:


i) 250 ml, 0.150 M HCl (Ans: 0.0375 mole)
ii) 6.72 liter H2 at STP. (Ans: 0.3 mole)

Hint: 1 mol of H2 at STP contain 22.4 L


EXERCISES
3. How many mole of solute present in the following
solutions:
i) 16.3 liter solution 0.113 M (Ans: 1.8419 mole)
ii) 15.6 ml solution 0.025 M (Ans: 0.0039 mole)

4. Calculate the molar concentration of ethanol in an aqueous


solution that contains 2.30 g of C2H5OH (46 g/mol) in 3.5 L of
solution
(Ans: 0.0143 M)

3. Calculate the molarity of 15.0 g ammonia in 750 mL


solution. (Ans: 1.1765 M)

4. Briefly explain how to prepare the following solutions; 500 mL


6.50 % (w/v) aqueous ethanol, C2H5OH.