University of Jordan Department of

Chemistry
Analytical Chemistry (0303211)
First I Semester 2020/2021

Course Information

Text Book: Fundamentals of Analytical Chemistry by

Skoog, West, Holler and Crouch; 9th Edition (2004)

Grading System:
Fquiz+Assignment 30 marks (To be announced later)
Second exam 30 marks (To be announced later)
Final Exam: 40 marks (To be announced later)
Total 100
Course Outline Based on 1-hour lectures [1]

No. of Topics
lectures
2 The Nature of Analytical Chemistry (Chapter 1)
5 Calculations Used in Analytical Chemistry
(Chapter 4)
3 Errors in Chemical Analysis (Chapter 5):
Some important terms, systematic errors,
3 Random Errors in Chemical Analysis ( Chapter
6):
The nature of random errors, statistical treatment of
random errors, standard deviation of calculated
results, reporting computed data,
2 Statistical Data Treatment and Evaluation
(Chapter 7): confidence intervals, detection of gross
errors
No. of Topics
lectures
5 Aqueous Solutions and Chemical Equilibria
(Chapter 9): classifying solutions of electrolytes,
chemical equilibrium, buffer solutions
3 Effect of Electrolytes on Chemical Equilibria
(chapter 10): The effect of electrolytes on
chemical equilibria, activity coefficients,
3 Solving equilibrium Problems for complex
systems (Chapter 11): solving equilibrium
problems by a systematic method, the solubility
of metal hydroxides, separation of ions by control
of the concentration of the precipitating agent
 Topics
6 Gravimetric Methods of Analysis (Chapter 12):
Precipitation gravimetry, calculation of results from gravimetric
data, applications of gravimetric methods
5 Titrimetric methods; Precipitation Titrimetry (Chapter 13):
Some terms used in volumetric titrimetry, standard solutions,
volumetric calculations, gravimetric titimetry, precipitation
titrimetry
4 Principles of Neutralization Titrations (Chapter 14):
Solutions and indicators for acid/base titrations, titration of
strong acids and strong bases, titration curves for weak acids,
titration curves for week bases, the composition of solutions
during acid/base titrations.
3 Complexation Reactions and Titrations (Chapter 17):
The formation of complexes, titrations with inorganic
complexing agents, organic complexing agents, aminocarboxylic
acid titrations
 Modified by
Dr. Mohammed Rasheed

ANALYTICAL CHEMISTRY

CHAPTERS 1 and 4 (REVIEW and

REVISION)

ANALYTICAL CHEMISTRY, MEASUREMENTS

STOICHIOMETRY, CONCENTRATIONS
 Role of Analytical Chemistry

• Analytical chemists use science and technology

to solve practical problems.

• Analytical chemistry is applied in all areas of

science, industry, and medicine.

• Chemistry: The Central Science; all sub-

disciplines rely on analytical chemistry to
function.
 ANALYTICAL CHEMISTRY
- Deals with the separation, identification, quantification,
and statistical treatment of the components of matter

Areas of Analytical Chemistry

Qualitative Analysis
- Deals with the identification of materials in a given sample
(establishes the presence of a given substance)
Quantitative Analysis
- Deals with the quantity (amount) of material
(establishes the amount of a substance in a sample)
Characterization analysis

Some analytical methods offer the three types of

information
 ANALYTICAL CHEMISTRY
Analytical Methods

- Gravimetry (based on weight)

- Titrimetry (based on volume)

- Electrochemical (measurement of potential, current, charge,

etc)

- Spectral (the use of electromagnetic radiation)

- Chromatography (separation of materials)

- Chemometrics (statistical treatment of data)

 ANALYTICAL CHEMISTRY
General Steps in Chemical Analysis

- Analysis
(measure the concentration of analyte in several identical portions)
(multiple samples: identically prepared from another source)
(replicate samples: splits of sample from the same source)

- Reporting and interpretation

(provide a complete report of results)

- Conclusion
(draw conclusions that are consistent with data from results)
Method Selection Criteria 1) Often from the literature
Base on Nature of Sample
and Goals -accuracy -
sensitivity –relialibility
2) Based on Practical
considerations -cost -time -
expertise

Our resulting # is never

absolutely CERTAIN.

An example of an analysis problem

Acquiring Sample

• Is the sample representative?

• Challenge: select a small sample of composition that accurately
represents the bulk
• Challenge: population size and heterogeneity

Processing Sample:
• To preserve sample integrity – Dry – Keep under inert
atmosphere
• To convert to a form suitable for measurements – Grind –
Dissolve – Oxidize, reduce, etc.
Eliminate interferences
• Interferents/ interferences: species other than the analyte that
affect the measurement.
• Matrix: all components in the sample containing the analyte.
• Solutions: remove or mask
Calibrating and Measuring

Calibration: process of determining the exact relationship

between the property measured and the property sought for
(Determination of k).
Generally, standards are used to calibrate a method.
 Ch. 4
MEASUREMENT

- Is the determination of the dimensions, capacity, quantity,

or extent of something

- Is a quantitative observation and consists of two parts:

a number and a scale (called a unit)

Examples
mass, volume, temperature, pressure, length, height, time
 MEASUREMENT SYSTEMS

Two measurement systems:

English System of Units (commercial measurements):

pound, quart, inch, foot, gallon

Metric System of Units (scientific measurements)

SI units (Systeme International d’Unites)
liter, meter, gram
More convenient to use
 FUNDAMENTAL SI UNITS

Physical Quantity Name of Unit Abbreviation

Mass Kilogram kg
Length Meter m
Time Second s (sec)
Temperature Kelvin K
Amount of substance Mole mol
Electric current Ampere A
Luminous intensity Candela cd
 DERIVED SI UNITS

Physical Quantity Name of Unit Abbreviation

Force Newton N (m-kg/s2)

Pressure Pascal Pa (N/m2; kg/(m-s2)
Energy Joule J (N-m; m2-kg/s2)
Power Watt W (J/s; m2-kg/s3)
Frequency Hertz Hz (1/s)
 METRIC UNITS

Prefix Abbreviation Notation

Giga G 109
Mega M 106
Kilo k 103
Deci d 10-1
Centi c 10-2
Milli m 10-3
Micro µ 10-6
Nano n 10-9
Pico p 10-12
Femto f 10-15
 UNIT CONVERSIONS

Length/Distance Time Volume Mass

2.54 cm = 1.00 in. 1 min = 60 sec 1 gal = 4 qt 1 Ib = 454 g

12 in. = 1 ft 1 hour = 60 min 1 qt = 0.946 L 1 Ib = 16 oz
1 yd = 3 ft 24 hours = 1 d 1 L = .0265 gal 1 kg = 2.20 Ib
1 m = 39.4 in. 1 mL = 0.034 fl. oz. 1 oz = 28.3 g
1 km = 0.621 mile
1 km = 1000 m

24 hours 1 day
24 hours = 1 day » 1 day or 24 hours
 TEMPERATURE
Celsius Scale (oC)
- Reference points are the boiling and freezing
points of water (0oC and 100oC)
- 100 degree interval

Kelvin Scale (K)

- Is the SI unit of temperature (no degree sign)
- The lowest attainable temperature on the Kelvin scale is 0
(-273 oC) referred to as the absolute zero

Fahrenheit Scale (oF)

- Water freezes at 32oF and boils at 212oF
- 180 degree interval
 TEMPERATURE

o o
K  C  273 or C  K  273

9 o
o 5
C  o F32  or
o
F   C  32
9 5
The Mole: The mole is the SI unit for the amount of chemical
species. The mole is associated with a chemical formula and
Avogadro’s number (6.022 x 1023) of particles. The molar mass
(M) of a substance is the mass in grams of one mole of the
substance. Molar masses are calculated by summing the atomic
masses of all the elements appearing in a chemical formula.

MOLAR MASS
- Add atomic masses to get the formula mass in
atomic mass unit (amu) = molar mass (in g/mol)

- That is the mass, in g, of 1 mole of the substance

1 mole = 6.02214179 x 1023 entities (atoms or molecules)
Usually rounded to 6.022 x 1023 (Avogadro’s number)
This implies that 6.022 x 1023 amu = 1.00 g
Atomic mass (amu) = mass of 1 atom
molar mass (g) = mass of 6.022 x 1023 atoms
 Molar Mass of formaldehyde CH2O
M CH 2O
1m olC 12 .0 g 2 m olH 1.0 g 1m olO 16 .0 g
     
m olC H 2 O m olC m olC H 2 O m olH m olC H 2 O m olO

 3 0 .0 g / m olC H 2 O

Molar Mass of glucose C6H12O6

M C 6 H 12 O 6
6 m olC 1 2 .0 g 1 2 m olH 1.0 g 6 m olO 1 6 .0 g
     
m olC 6 H 1 2 O 6 m olC m olC 6 H 1 2 O 6 m olH m olC 6 H 1 2 O 6 m olO

 1 8 0 .0 g / m olC 6 H 1 2 O 6
MOLAR MASS
Q4-1Calculate the mass of 2.4 moles of NaNO3
 Mass and Weight: Mass is an invariant measure of the
amount of matter in an object. Weight is the force of
attraction between an object and earth. The weight of an
object depends on the location because gravitational
attraction varies with geographic location. The mass of an
object remains constant regardless of locations. A
chemical analysis is always based on mass so that the
results will not depend on locality.

The Millimole: The millimole (mmol) is 1/1000 of a mole.

Sometimes it is more convenient to make calculations with
millimoles (mmol) rather than mole. The mass in grams of a
millimole of a substance is known as the millimolar mass
which is 1/1000 of the molar mass
1 mmol = 10-3 mol
Q4-2: Determine the number of moles and millimoles of
benzoic acid (C6H5COOH) (M = 122.1 g/mol) in 2.00
g of the pure acid.
Q4-3: Determine the mass in grams of Na+ (22.99
g/mol) in 25.0 g of Na2SO4(142.0 g/mol).

1 m o l N a 2S O 4
A m o u n t fo N a = 2 5 .0 g N a 2 S O 4 
1 4 2 .0 g N a 2 S O 4
2 +m o l N a 2 2.9 9 g N a
 
1 m o l N a 2S O 4 1 m ol N a
+ +

 8 .1 0 g N a +

+
CONCENTRATION OF SOLUTIONS
 The amount of solute dissolved in a given quantity of
solvent or solution
Molar concentration (Molarity M)
 The number of moles of solute per liter of solution

moles solute mmolessolute

Molarity  
volume of solution L  volume of solution mL

 A solution of 1.00 M (read as 1.00 molar) contains 1.00

mole of solute per liter of solution
Q 4-4: Calculate the molar concentration of ethanol in an
aqueous solution that contains 2.30 g of C2H5OH (46.07
g/mol) in 3.50 L of solution.
Q4-5: After dissolving 1.56 g of NaOH in a certain volume of
water, the resulting solution had a concentration of 1.60 M.
Calculate the volume of the resulting NaOH solution?
CONCENTRATION OF IONS
1.00 M NaCl: 1.00 M Na+ and 1.00 M Cl-
1.00 M ZnCl2: 1.00 M Zn2+ and 2.00 M Cl-
1.00 M Na2SO4: 2.00 Na+ and 1.00 M SO42-

Q4-6: Calculate the number of moles of Na+ and SO42-

ions in 1.50 L of 0.0150 M Na2SO4 solution
 Analytical Molarity: The analytical molarity of a
solution gives the total number of moles of a solute in 1L
of the solution (or total number of millimoles in 1 mL). A
1.0 M H2SO4 can be prepared by dissolving 1.0 mol or 98 g
of H2SO4 in water and diluting to exactly 1.0 L.

 Equilibrium Molarity: The equilibrium molarity or

species molarity express the molar concentration of a
particular species in a solution at equilibrium. The
equilibrium molarity of H2SO4 in a solution with an
analytical concentration of 1.0 M is 0.0 M because H2SO4
is entirely dissociated, there are no H2SO4 molecules as
such in this solution.
Q4-7: Calculate the analytical and equilibrium molar
concentrations of the solute species in an aqueous solution
that contains 285 mg of trichloroacetic acid (HA),
Cl3CCOOH (163.4 g/mol) in 10.0 mL. Trichloroacetic acid
(HA) is 73% ionized in water.
Q4-8

Q4-9
DILUTION
- Consider a stock solution of concentration M1 and
volume V1
- If water is added to dilute to a new concentration M2 and
volume V2
- moles before dilution = moles after dilution
- Implies that M1V1 = M2V2
Example: Calculate the volume of 3.50 M HCl needed to prepare 500.0
mL of 0.100 M HCl
Percent concentration: Concentration can be expressed in
terms of percent (parts per hundred). Percent composition
can be expressed in three different methods:
Parts Per Million and Parts Per Billion: For very
dilute solutions, parts per million (ppm) is a convenient
way to express concentration.

Cppm = (mass of solute)/(mass of solution) x 106 ppm

where, Cppm is the concentration in parts per million.

For even more dilute solution parts per billion is used

Cppb =(mass of solute)/(mass of solution) x 109 ppb
Q4-10: A sugar solution is made by dissolving 5.8 g of sugar
in 82.5 g of water. Calculate the percent by mass
concentration of sugar.

Q4-11: Calculate the volume percent of solute if 345 mL of

ethyl alcohol is dissolved in enough water to produce 1257 mL
of solution

Q4-12: If 0.250 L of aqueous solution with a density of 1.00 g/mL

contains 13.7 μg of pesticide, express the concentration of pesticide
in ppm

Q4-13: What is the molarity of K+ in a solution that contains

63.3 ppm of K3Fe(CN)6 (329.3 g/mol)?
 Density
The density of a substance is its mass per unit
volume. Density is expressed in units of kg/L or
g/mL.

Specific Gravity
Specific gravity is the ratio of its mass to the mass
of an equal volume of water at 4oC. Specific
gravity is dimensionless.
Q4-14: Calculate the molar concentration of HNO3 (63.0
g/mol) in a solution that has a specific gravity of 1.42 and is
70% HNO3 (w/w).
Q4-15
Q4-16

Q4-17

Q4-18
 CHEMICAL FORMULA

Consider Na2S2O3:

- Two atoms of sodium, two atoms of sulfur, and three atoms of

oxygen are present in one molecule of Na2S2O3

- Two moles of sodium, two moles of sulfur, and three moles of

oxygen are present in one mole of Na2S2O3
 CHEMICAL FORMULA
How many moles of sodium atoms, sulfur atoms, and oxygen
atoms are present in 1.8 moles of a sample of Na2S2O3?

I mole of Na2S2O3 contains 2 moles of Na, 2 moles of S, and 3

moles of O
2 moles Na atoms
moles Na atoms  1.8 moles Na 2S2 O 3 x  3.6 moles Na atoms
1 mole Na 2S 2 O 3

2 moles S atoms
moles S atoms  1.8 moles Na 2S 2 O 3 x  3.6 moles S atoms
1 mole Na 2S 2 O 3

3 moles O atoms
moles O atoms  1.8 moles Na 2S2 O 3 x  5.4 moles O atoms
1 mole Na 2S2 O 3
 CHEMICAL CALCULATIONS
Calculate the number of molecules present in 0.075 g of urea,
(NH2)2CO

Given mass of urea:

- convert to moles of urea using molar mass
- convert to molecules of urea using Avogadro’s number

1 mole (NH 2 ) 2 CO 6.022 x 1023 molecules ( NH 2 ) 2 CO

0.075 g (NH 2 ) 2 CO x x
60.07 g (NH 2 ) 2 CO 1 mole (NH 2 ) 2 CO

= 7.5 x 1020 molecules (NH2)2CO

 CHEMICAL CALCULATIONS
How many grams of carbon are present in a 0.125 g of vitamin C,
C6H8O6

Given mass of vitamin C:

- convert to moles of vitamin C using molar mass
- convert to moles of C (1 mole C6H8O6 contains 6 moles C)
- convert moles carbon to g carbon using atomic mass
1 mol C 6 H 8O 6 6 mol C 12.01g C
0.125 g C 6 H 8O 6 x x x
176.14 g C 6 H 8O 6 1 mol C 6 H 8O 6 1 mol C

= 0.0511 g carbon
 CHEMICAL EQUATIONS
(STOICHIOMETRIC CALCULATIONS)

Given:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)

- 1 molecule of C3H8 reacts with 5 molecules of O2 to

produce 3 molecules of CO2 and 4 molecules of H2O

- 1 mole of C3H8 reacts with 5 moles of O2 to produce

3 moles of CO2 and 4 moles of H2O
 CHEMICAL EQUATIONS
(STOICHIOMETRIC CALCULATIONS)
Given:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
What mass of oxygen will react with 96.1 g of propane?

- make sure the equation is balanced

- calculate moles of propane from given mass and molar mass
- determine moles of oxygen from mole ratio (stoichiometry)
- calculate mass of oxygen
1 mol C 3 H 8 5 mol O 2 32.00 g O 2
96.1 g C 3 H 8 x x x
44.11 g C 3 H 8 1 mol C 3 H 8 1 mol O 2

= 349 g O2
 CHEMICAL EQUATIONS
(STOICHIOMETRIC CALCULATIONS)
Given:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
What mass of CO2 will be produced from 96.1 g of propane?

- make sure the equation is balanced

- calculate moles of propane from given mass and molar
mass
- determine moles of CO2 from mole ratio (stoichiometry)
- calculate mass of CO2
1 mol C 3 H 8 3 mol CO 2 44.01 g CO 2
96.1 g C 3 H 8 x x x
44.11 g C 3 H 8 1 mol C 3 H 8 1 mol CO 2

= 288 g CO2
CONCENTRATION OF SOLUTIONS

Mole Fraction (χ)

- Fraction of moles of a component of solution

moles of component
 
total moles of all components

The sum of mole fractions of all components = 1

 CONCENTRATION OF SOLUTIONS

Given that the total moles of an aqueous solution of NaCl and

other solutes is 1.75 mol. Calculate the mole fraction of NaCl
if the solution contains 4.56 g NaCl.

1 mole NaCl
Moles NaCl  4.56 g NaCl x  0.0780 mol NaCl
58.44 g NaCl

0.0780 mol NaCl

mole fraction   0.0446
1.75 mol total
 MOLALITY (m)

Moles of solute per kg of solvent

Unit: m or molal

moles solute
m
kg solvent
 MOLALITY (m)
What is the molality of a solution that contains
2.50 g NaCl in 100.0 g water?

- Calculate moles NaCl

- Convert g water to kg water
- Divide to get molality
1 mole NaCl
moles NaCl  2.50 g NaCl x  0.0428 mol NaCl
58.44 g NaCl

0.0428 mol NaCl

molality   0.428 m NaCl
0.1000 kg solvent
CONVERTING CONCENTRATION UNITS
Calculate the molality of a 6.75 %(m/m)
solution of ethanol (C2H5OH) in water

Mass water = 100 g solution – 6.75 g ethanol = 93.25 g water

6.75 g ethanol
Mass percent ethanol 
100 g solution

mol ethanol (6.75 /46.08) mol

molality    1.57 m ethanol
kg solvent (93.25/1000) kg
CONVERTING CONCENTRATION UNITS
Calculate the mole fraction of a 6.75 %(m/m)
solution of ethanol (C2H5OH) in water

Mass water = 100 g solution – 6.75 g ethanol = 93.25 g water

1 mol
moles ethanol  6.75 g ethanol x  0.146 mol
46.08 g
1 mol
moles water  93.25 g water x  5.17 mol
18.02 g

mol component 0.146 mol

mol fraction    0.0275
total moles (0.146  5.17) mol
CONVERTING CONCENTRATION UNITS

Practice Question

Given that the mole fraction of ammonia (NH3) in water is 0.088

Calculate the molality of the ammonia solution
CONVERTING CONCENTRATION UNITS
- Molarity is temperature dependent
(changes with change in temperature)
- Volume increases with increase in temperature
hence molarity decreases

On the other hand

- Molality
- Mass percent
- Mole fraction
are temperature independent
 CHEMICAL EQUILIBRIUM
- Occurs when there is product build-up during a chemical reaction
- The product molecules interact with one another to
re-produce reactants
forward reaction

A + B C + D
reverse reaction

Chemical Equilibrium
- When the rate of product formation (forward reaction)
is equal to the rate of reactant formation (reverse reaction)
 CHEMICAL EQUILIBRIUM

- Reactant and product concentrations are usually not equal

- Such reactions are known as reversible reactions

- Forward reaction rate decreases with time as

reactants are used up

- Reverse reaction rate increases with time as

products are being formed

- Concentrations are reached when both forward

and reverse rates become equal
 EQUILIBRIUM CONSTANT

- Describes the extent of reaction in a given system

- For a chemical reaction of the form

aA + bB → cC + dD

- The equilibrium constant (Keq) is given by

[C]c [D]d
K eq 
[A]a [B]b
 EQUILIBRIUM CONSTANT

- [ ] denotes concentration in moles/liter (M)

- Product concentrations in the numerator

- Reactant concentrations in the denominator

- Concentrations are raised to the powers of the

respective coefficients

- Gases (in bars) and substances in solution (in mol/L)

are written in Keq expressions
 EQUILIBRIUM CONSTANT

- Pure solids, pure liquids (e.g. water), and solvents are not
written since they are constant

- Keq changes with change in temperature

- For exothermic forward reactions (heat released)

Keq decreases with increasing temperature

- For endothermic forward reactions (heat absorbed)

Keq increases with increasing temperature
 EQUILIBRIUM CONSTANT
Large Keq
- Greater product concentrations than reactant concentrations
- Equilibrium position lies to the right

Small Keq
- Smaller product concentrations than reactant concentrations
- Equilibrium position lies to the left

Intermediate Keq (near unity)

- Both products and reactants are in significant amounts
- Equilibrium position lies neither to the right nor to the left
 EQUILIBRIUM CONSTANT

- Longer arrows can be used to indicate the predominant species

- Longer forward reaction arrow for large Keq

- Longer reverse reaction arrow for small Keq

CO2 + H2O H2CO3

 LE CHATELIER’S PRICIPLE

- If a stress (change of conditions) is applied to a system in

equilibrium the system will readjust (change the equilibrium
position) in the direction that best reduces the stress imposed
on the system

- If more products form as a result of the applied stress

the equilibrium is said to have shifted to the right

- If more reactants form as a result of the applied stress

the equilibrium is said to have shifted to the left
 LE CHATELIER’S PRICIPLE
Concentration Changes

For a reaction mixture at equilibrium

- Addition of reactant(s) shifts the equilibrium position to the right

- Removal of product(s) shifts the equilibrium position to the right

- Addition of product(s) shifts the equilibrium position to the left

- Removal of reactant(s) shifts the equilibrium position to the left

 LE CHATELIER’S PRICIPLE

Temperature Changes

Exothermic Reactions

- Heat is a product

- Increase in temperature shifts the equilibrium position to the left

- Decrease in temperature shifts the equilibrium position to the right

 LE CHATELIER’S PRICIPLE

Temperature Changes

Endothermic Reactions

- Heat is a reactant

- Increase in temperature shifts the equilibrium position to the right

- Decrease in temperature shifts the equilibrium position to the left

 LE CHATELIER’S PRICIPLE

Pressure Changes

- Gases must be involved in the chemical reaction

- The total number of moles of the gaseous state must change

- Equilibrium is shifted in the direction of fewer moles

 LE CHATELIER’S PRICIPLE

Pressure Changes

Higher moles of gaseous reactants than products

- Increase in pressure shifts the equilibrium position to the right
- Decrease in pressure shifts the equilibrium position to the left

Higher moles of gaseous products than reactants

- Increase in pressure shifts the equilibrium position to the left
- Decrease in pressure shifts the equilibrium position to the right
 LE CHATELIER’S PRICIPLE

Pressure Changes

No change in equilibrium position occurs if

- There is no reactant nor product in the gaseous state

- Number of moles of gaseous reactants equals number of

moles of gaseous products

- Pressure is increased by adding a nonreactive (inert) gas

 LE CHATELIER’S PRICIPLE

Addition of Catalysts

- Catalysts do not change equilibrium positions

- Catalysts speed up both forward and reverse reactions so have

no net effect

- Catalysts allow equilibrium to be established more quickly by

lowering the activation energy