SCH 2100: ATOMIC STRUCTURE

JOMO KENYATTA UNIVERSITY

OF
AGRICULTURE AND TECHNOLOGY
1 MEASUREMENTS AND FUNDAMENTAL TERMS IN CHEMISTRY
1.1 Atomic Weight
Atomic weight, also called relative atomic mass, ratio of the average mass of a chemical
element’s atoms to some standard. The standard unit of atomic mass has been one-twelfth
the mass of an atom of the isotope carbon-12.
An isotope is one of two or more species of atoms of the same chemical element that
have different atomic mass numbers (protons + neutrons).
The atomic weight of helium is 4.002602, the average that reflects the typical ratio of
natural abundances of its isotopes. Atomic weight is measured in atomic mass units
(amu), also called Dalton’s.
The concept of atomic weight is fundamental to chemistry, because most chemical
reactions take place in accordance with simple numerical relationships among atoms.
The table provides a list of chemical elements and their atomic weights:

Hydrogen H 1 [1.00784, 1.00811]

Helium He 2 4.002602

Lithium Li 3 [6.938, 6.997]

Beryllium Be 4 9.0121831

Boron B 5 [10.806, 10.821]

Carbon C 6 [12.0096, 12.0116]

Nitrogen N 7 [14.00643, 14.00728]

Oxygen O 8 [15.99903, 15.99977]

fluorine F 9 18.998403163

Neon Ne 10 20.1797

Sodium Na 11 22.98976928

Magnesium Mg 12 [24.304, 24.307]

Aluminum Al 13 26.9815385

Silicon Si 14 [28.084, 28.086]

Phosphoru
s P 15 30.973761998

Sulfur
(Sulphur) S 16 [32.059, 32.076]

Chlorine Cl 17 [35.446, 35.457]

Argon Ar 18 39.948

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1.2 Mole Concept
The mole is an amount unit similar to familiar units like pair, dozen, gross, etc. It provides a
specific measure of the number of atoms or molecules in a bulk sample of matter. A mole is
defined as the amount of substance containing the same number of discrete entities
(atoms, molecules, ions, etc.) as the number of atoms in a sample of pure 12C weighing
exactly 12 g. One Latin connotation for the word “mole” is “large mass” or “bulk,” which is
consistent with its use as the name for this unit. The mole provides a link between an easily
measured macroscopic property, bulk mass, and an extremely important fundamental
property, number of atoms, molecules, and so forth.
The number of entities composing a mole has been experimentally determined to be
6.02214179×1023, a fundamental constant named Avogadro’s number (NA) or the
Avogadro constant in honor of Italian scientist Amedeo Avogadro. This constant is properly
reported with an explicit unit of “per mole,” a conveniently rounded version being
6.022×1023/mol
Consistent with its definition as an amount unit, 1 mole of any element contains the same
number of atoms as 1 mole of any other element. The masses of 1 mole of different elements,
however, are different, since the masses of the individual atoms are drastically different. The
molar mass of an element (or compound) is the mass in grams of 1 mole of that substance, a
property expressed in units of grams per mole (g/ mol).

In most of chemical calculations, we are more interested in the number of atoms, ions or
molecules present than in the mass of the sample or volume of the solution. Chemists report
numbers of atoms, ions and molecules in terms of moles. This is a unit which can be
compared to the unit dozen in wholesale implying 12 items.

Similarly, a mole (abbreviated to “mol”) can be defined as the number of atoms in exactly

12 grams of carbon-12. The mass of a carbon-12 (or 12carbon) atom has been found (using
Mass Spectrometry) to be 1.99265× 10-23 g .
Thus, it follows that the number of atoms in 12 g of carbon-12 is;
12 g 23
-23
= 6.022×10 atoms
1.99265× 10 g

Because the mole gives the number of atoms in any given sample, it follows that one mol of
atoms of any element is 6.022× 1023 atoms of that element. This applies for 1 mol of any
objects, be they atoms, ions or molecules.
The value 6.022× 1023 denotes the number of objects per mole (6.022× 1023 mol−1) and is
called Avogrado Constant, NA. It is named after the 19th century Italian scientist Amedeo
Avogrado. Thus, one mole of substance contains the Avogrado number (N A) of particles.
Another symbol of the Avogrado Constant is L.

NB: One mole of a substance is the Relative atomic mass (RAM) or relative molecular mass
(RMM) of that substance in grams.
Examples

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 (1).1 mol of sulfur atoms will weigh 32g
(2).1 mol of water (H2O) will weigh 18g [(1 x 2) + 16 = 18g]
(3). 0.2 mol of calcium carbonate (CaCO3) will weigh 20g [Since RMM of CaCO3 is
100g, 0.2 mol will be 0.2 x 100 = 20g]
(4). Vitamin C is known to contain 1.29 x 1024 atoms of Hydrogen. Thus the moles of
Hydrogen in Vitamin C will be found by;
No. of atoms = No. of moles x NA
N = n x NA

Thus,

(5) How many calcium ions and chloride ions are in 0.5 mol Calcium chloride (CaCl2)?
Solution
CaCl2 Ca2+ + 2Cl-
From the dissociation equation (i.e. theoretically), we see that for every mole of CaCl 2, 1
mol of Ca2+ ions and 2 moles of Cl- ions are produced.
Hence;
CaCl2 Ca2+ + 2Cl-
0.5 mol 0.5 mol 1 mol
0.5 mol Ca2+ ions = 0.5 x NA = 3 x 1023 ions

1 mol Cl- ions = 1 x NA = 6 x 1023 ions

For any sample with a molar mass;

1.3 Molarity
Molarity is defined as the moles of a solute per liters of a solution. Molarity is also known
as the molar concentration of a solution. Molarity (M) indicates the number of moles of
solute per liter of solution (moles/Liter) and is one of the most common units used to
measure the concentration of a solution. Molarity can be used to calculate the volume of
solvent or the amount of solute

In chemistry, concentration of a solution is often measured in molarity (M), which is the

number of moles of solute per liter of solution.
The SI unit for molar concentration is mol/m 3. However, mol/L is a more common unit for
molarity. A solution that contains 1 mole of solute per 1 liter of solution (1 mol/L) is called
“one Molar” or 1 M. The unit mol/L can be converted to mol/m 3 using the following
equation:

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1 mol/L = 1 mol/dm3 = 1 mol dm−3 = 1 M = 1000 mol/m3

To calculate the molarity of a solution, the number of moles of solute must be divided
by the total liters of solution produced. If the amount of solute is given in grams, we
must first calculate the number of moles of solute using the solute’s molar mass, then
calculate the molarity using the number of moles and total volume.
Molarity of a given solution is given by the number of moles of substance dissolved in one
liter of solution. It is denoted by M, and it is read as “molar”.

Units of molarity are moles per liter (molL-1 or mol/L).

Molarity of a solution can be calculated from the mass of solute dissolved in the solution.

Examples (Students to work out)

(6). Calculate molarity of 12g of sodium chloride (NaCl) dissolved in 250 ml of water (Ans;
0.821 M)
(7). Give the mass of silver nitrate (AgNO3) contained in 40ml of a 0.05M solution of the
salt (Ans; 0.34g)
(8). In an analysis of alcohol, a chemist needs to prepare 1 L of 0.200M of potassium
dichromate (K2Cr2O7). What mass of potassium dichromate is he needed to weigh? (Ans;58.8 g)
(9). The empirical formula of a compound is C10H18O. Determine the molecular formula of a
compound with a molar mass of 462 g/mol
To determine the molecular formula;
( C10 H18 O ) n=462
Mass of the empirical unit will be
C10 H18 O = 10 ( 12 ) +18 ( 1 )+ 16=154
So we have
154 n=462
Solving for n
462
n= =3
154
The molecular formula will then be given by replacing n in (C10H18O) n with 3, to get
C30 H54 O3

(8).3.94g of hydrated copper II sulfate left 2.52g of the anhydrous salt after prolonged

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heating. Give the degree of hydration of this salt (i.e. the number of water molecules in the
formula).
CuSO 4 ∙ X H 2 O→ CuSO 4 + X H 2 O
(3.94 g) (2.52 g) (1.42 g)
CuSO 4 H2 O
Dividing by molar masses 2.52 1.42
=0.01579 =0.07889
159.609 18

0.01579 0.07889
Dividing by smallest value all =1 =5.00
0.01579 0.01579
through

Thus, H2O moles are 5 (degree of hydration); CuSO 4 ∙5 H 2 O

(9). A certain chemical that causes a severe skin disease is composed 44.2% C, 43.5% Cl,
9.82% O and 2.48% H. It has a molar mass of 326g/mol. Determine its empirical formula and
its molecular formula.
Solution
C Cl O H
Dividing by 44.2 43.5 9.82 2.48
=3.68 =1.225 =0.61375 =2.48
12 35.5 16 1
molar masses

Dividing by 2.48
3.68 1.225 0.61375 =4
=6 =2 =1 0.61375
smallest value 0.61375 0.61375 0.61375
all through
Thus, the empirical formula will be given as C6H4Cl2O.
For the molecular formula; (C6H4Cl2O) n = 326
Adding up the masses in the empirical formula, 163n =326;
n=2;
Leading to C12H8Cl4O2.

1.4 Dilution

To save on space and time, solutions and reagents are stored as stock solutions. Whenever a
certain concentration is needed, portions are withdrawn from the stock solutions and diluted.
Thus, an ability to dilute solutions accurately is needed in the laboratory. Instruments such as
pipettes, burets and syringes aid in dilution, as very small volumes may be needed. It is
important to note that when a small volume of a solution is diluted to a larger volume, the

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total number of moles of the solute remains constant; it is only the concentration which
reduces. The expression below is used in dilution;

Mi and Vi are the Molarity and volume of the initial solution respectively, Mf and Vf are the
Molarity and volume of the final solution respectively.
Thus, to determine the amount of volume you need to withdraw from the stock (starting)
solution, we make Vi the subject of the formula;

In most of the times, the final volume is the volume of the holding container (volumetric
flask etc.) but this may not always be the case.
Example (12)

Suppose we wanted to know the volume of 0.0380 M KMnO 4 solution that we should use to
prepare 250 ml of 1.5 x 10-3 M KMnO4 solution. We use the dilution equation and rearrange
it to give

Then we simply substitute the data

You may use any unit (for both the concentration and volume) in this formula, provided
you ensure uniformity on both sides.

Example (13)

When titrating 1M of sulfuric acid with an unknown concentration of sodium hydroxide

using an indicator, exactly 25ml of the base were used. The volume of the acid used was
10 ml.

a. Determine the number of moles of acid used

H2SO4(aq) + 2NaOH (aq) Na2SO4 (aq) + 2H2O(l)

Since 1.0 mol is contained in 1000 ml, 10 ml will contain;

b. Determine number of moles of the base

Since the mole ratio (acid:base) is 1:2

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 Moles of base will be twice those of acid, thus 0.01 x 2 = 0.02 mol

c. Determine the molarity of the base

Example (14)
Hydrated oxalic acid (H2 C2 O4 ∙2 H2 O) was made by dissolving 0.63 g of the acid in 250 mL
water. 25 mL of this solution were used to titrate against sodium hydroxide (NaOH). If 26.5
mL of NaOH were used in the reaction;
a. Calculate the number of moles of oxalic acid used
H 2 C2 O4 ∙2 H 2 O(aq )+ NaOH (aq ) → Na2 C2 O4( aq) + 2 H 2 O( aq)

Since 0.63 g were dissolved in 250 mL, mass of oxalic acid dissolved in 1 L
1000 mL /L
Mass per liter=0.63 g × =2.52 g/ L
250 mL

RMM of hydrated oxalic acid is 126

Mass per liter 2.52
Molarity= = =0.02 M
RMM 126

Number of moles of acid used

25 −4
n=0.02 M × =5.8 ×10 mol
1000

b. Calculate number of moles of NaOH used

From the reaction equation, the ratio of acid:base is 1:2, This gives the moles of base
as double those of acid,
−4 −3
5.8 ×10 mol ×2=1.16 ×10 mol
c. Calculate the concentration of the base in;

i. Molarity
−3 −3
n 1.16 × 10 mol 1.16 ×10 mol
Molarity= = = =0.04 M
V ∈liters
(
26.5 mL
1000 mL /L )
0.0265 L

ii. Mass per liter (grams/Liter)

mol g
Mass per liter=Molarity × RMM =0.04 × 40 =1.6 g/ L
L mol
d. If the sodium hydroxide was used to determine an unknown concentration of
hydrochloric acid (HCl), in which 25ml of the acid were used and 2ml of the base were

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 used. Determine the following;
i. The moles of NaOH used in the reaction
2 −5
n=M × V =0.04 × =8× 10 mol
1000

ii. Moles of the HCl used in the reaction

Reaction eqn: HCl (aq )+ NaOH (aq) → NaCl(aq ) + H 2 O (aq )
From the equation between the two, the ratio is 1:1, so the acid will have
an equal
number of moles as the base, 8 ×10−5 mol
iii. The concentration of the acid in;

a. Molarity
−5
n 9× 10 mol
Molarity= = =0.0032 M
V 25
(
1000 )
b. Mass per liter
mol g
Mass per liter=Molarity × RFM=0.0032 ×36.5 =0.1168 g / L
L mol

2 ACID AND BASES

Arrhenius definition of an acid is a substance that provides hydrogen ions, H +, when dissolved in
water, and one definition of a base is a substance that provides hydroxide ions, OH -, when dissolved
in water. Arrhenius definition of a base is restricted to those substances which react with H + ion to
form water.
In order to widen the scope of acid- base reaction and include non-aqueous systems and a wider range
of bases, Brønsted and Lowry independently suggested the following definition in 1923.

An acid is a proton donor while a base is a proton acceptor,

Thus, the relationship between an acid and its corresponding base is

HB and B- are said to be conjugate and to form conjugate acid – base pair. HB is the conjugate acid
of B- and B- is the conjugate base of HB.

According to Brønsted–Lowry theory acid salts such as NaHSO 4 and ammonium ion (NH4+) are
recognized as acid. What is more the definition of a base including: all anions, water and ammonia as

9
well as oxides and hydroxides.

NB/ On the equations above, water can act as a base and as an acid. It does this simultaneously
during its dissociation.

2.1 Lewis Definition

Lewis acid - accept pair of electrons to form a covalent bond, for example BCl 3 and AlCl3. Whereas
Lewis base – donate pair of electrons to form a covalent bond, for example NH 3, CH3NH2.
Soft acids - large cations with low charge density. e.g. Cs+ and Fr+.
Soft bases - large anions with low charge density. e.g. I-.
Hard acids - small cations with high charge density. e.g. Al3+.
Hard bases - small anions with high charge density. e.g. F-.

2.2 Ionic Equilibrium in Aqueous Solutions

Equilibrium involving ions in aqueous solution are important in industrial analytical and biological
processes. The principles and characteristics of these ionic equilibria are very similar to those in other
systems in chemical equilibria.
Two fundamental types of ionic equilibrium:
1. Equilibrium between undissolved solid solute and its dissolved product in solution are
solubility equilibrium.
2. The equilibrium between dissolved undissociated molecules and its dissolved ions, i.e.
dissociation equilibria.

In most cases this dissociation equilibria involve either acids or bases.

2.3 The Strength of the Acids and Bases

The strength of the acid is a measure of extent of dissociation.

The strength of different acids or bases can be compared using conductivity measurements.

Strong electrolytes such as HCl and NaOH are almost completely dissociated into ions in aqueous
solution. For example

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 Almost completely dissociated or ionized
Strong acid

Almost completely dissociated or ionized

Strong base

Weak acids and bases are only partially ionized. For example

Ethanoic acid Only partially dissociated or ionized

weak acid

Only partially dissociated or ionized

Weak base

2.4 Quantitative Measurement of pH

In case of acids, relative strength can be compared by measuring the concentration of hydrogen ions
or by measuring their pH.

The “p” in pH comes from German word “potenz” meaning power and “H” from [H +] concentration
of hydrogen.

The pH of a solution is the negative logarithm to base 10 of the molar hydrogen ion concentration i.e.
+
( aq )
pH =−lg [ H ]

Notice that the accepted abbreviation for logarithm to base 10 is lg not log.

Some useful mathematical expressions

lg xy=lg x +lg y
x
lg =lg x−lg y
y

lg x n =n lg x

For example,
lg 10 2=0 . 3010 implying 100 . 3010=2

[H+] concentration in aqueous solution ranges from 10-15 to 10 mol dm-3, so it is convenient to have a
scale that is both negative and antilogarithmic. The negative sign produces positive pH values for
almost all solutions encountered in practice.

The logarithmic scale reduces the extremely wide variation in [H +(aq)] concentration to a narrow range
of pH from about 15 to -1.

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Some worked examples
1. What is the pH of 10-1 mol dm-3 HCl (0.1 M HCl)?

Solution
Since HCl is fully dissociated and monobasic acid
[H+(aq)] in 10-1 mol dm-3 HCl=10-1 mol dm-3
+
( aq )
pH =−lg [ H ]=−lg 10−1
=(−1)lg 10
=(-1)(-1)=+1

2. What is the pH of 10-3 mol dm-3 H2SO4 (0.001 M H2SO4)?

Since H2SO4 is fully dissociated and dibasic acid
[H+(aq)] in 10-3 mol dm-3 H2SO4=2x10-3 mol dm-3
+
( aq )
pH =−lg [ H ]=−lg ( 2 x 10−3 )
3
=(−1)lg 2 x 10
=(-1)(0.30-3)=+2.7

3. The pH of pure water at 25 °C is 7. What is the hydrogen ion concentration?

Solution
+
( aq )
pH =−lg [ H ]
+
( aq )
7=−lg [ H ]
+
( aq )
Therefore lg [ H ]=−7
[H (aq)]=10 =1x10-7
+ -7

Study questions

What are the pH values of the following solutions?

a) 10-3 mol dm-3 HCl
b) 1.0 mol dm-3 HCl
c) 3 M HX which is only 50% dissociated

3 REDOX REACTIONS
Oxidation is defined as loss of one or more electron(s) by a substance, element, compound or ion
Whereas

Reduction is defined as gain of one or more electron(s) by a substance, element, compound or ion.

Thus an oxidation – reduction reaction or REDOX reaction is a process in which electrons are
transferred from one substance to another.

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3.1 How Can We Tell When Redox Reaction is Taking Place?
We assign to atom a substance a value called oxidation number or oxidation state, which provides a
measure of an atom is neutral, electron rich or electron poor. By comparing oxidation number of an
atom before and after reaction, we can tell whether atom has gained or lost one or more electron(s).

NB/ Oxidation number does not necessarily imply ionic charges. They are simply convenient device
to help us keep track of electrons in redox reaction. Whenever one substance lose one or more
electron(s) (oxidized) another substance must gain electron(s) (be reduced).

Reducing agent
Reducing agent loses one or more electron(s).
 undergo oxidation or
 Oxidation number of atom increase.

Oxidizing agent
Reducing agent gains one or more electron(s).
 undergo reduction or
 Oxidation number of atom decrease.

3.2 Balancing Redox Reaction

There are two system approach often used for balancing redox reaction:

I. The oxidation number method.

II. The half-reaction method.

3.2.1 Balancing Redox Reaction by Oxidation Number Method

The key to the oxidation-number method of balancing redox equation is to realize that the net charge
in the total of all oxidation number must be zero. That is any increase in oxidation number for the
oxidized atoms must be exactly matched by a corresponding decrease in oxidation number of the
reduced atoms.

Steps used in balancing a redox reaction by the oxidation number method

1. Write the unbalanced ionic equation.
2. Balance the equation for all atoms other than H and O.
3. Assign oxidation number to all atoms.
4. Decide which atom have changed oxidation number and by how much.
5. Find the total net increase in oxidation number for the oxidized atoms and the total net
decrease in oxidation number for the reduced atoms. Multiply the net increase and the net
decrease by a suitable number so that the two values become equal.
6. Balance the equation for oxygen by adding H 2O to the side with less O and then balance for
hydrogen by adding H+ to the side with less H. Check your answer by making sure that the
equation is balanced both for atom and for charge.

Total increase in oxidation =Total decrease in oxidation Is equivalent as saying that the
number (oxidation) number (Reduction) total loss and gain of electron(s)
are equal in redox reaction

Worked example
Balance the following redox reaction.
An aqueous acidic solution of the purple permanganate anion MnO 4- is reduced by Br- to yield the
pale pink Mn2- ion along with Br2.

1 The unbalanced ionic equation for the process is:

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2 Balance the equation for all atoms other than H and O. Add a coefficient 2 for Br- to

3 Assign oxidation numbers

4 Decide which atom have changed oxidation number and by how much

5
Increase in oxidation numbers 2x(Br-1Br0) net increase +2.

Decrease in oxidation numbers 2x(Mn+7Mn+2) net decrease -5.

LCM of 2 and 5=10

6 Balance for O by adding H2O to the side with less O and then balance it by adding H+ to
the side with less H.

Charge: LHS: (2x-1)+(10x-1)+(16x+1)=+4 RHS: (2x+2)=+4

If everything has been done correctly, the final net ionic equation will result. The answer can be
checked by noting that the equation is balanced both for atom and for charge with +$ on both sides.

3.2.2 Balancing Redox Reaction the Half-Equation Method

The key to this method is to realize that the overall reaction can be broken into two parts or half-
reaction. One half-reaction describes the oxidation part of the process and the other half-reaction

14
describes the reduction part. Each half is balanced separately and the two halves are then added to
obtain the final equation.
Steps used in balancing a redox reaction by half-reaction method
1. Write the unbalanced ionic equation
2. Decide which atoms are oxidized and which are reduced and write two unbalanced half-
reaction for the separate process.
3. Balance both half-reaction for all atoms other than H and O.
4. Balance both half-reaction for O by adding H2O to the side with less O and then balance for H
by adding H+ to the side with less H.
5. Balance both half-reactions for charge by adding electrons (e -) to the side with the greatest
positive charge. Then multiply the half-reactions by suitable number to make the electrons
count the same in both.
6. Add the two balanced half-reaction and cancel the electrons and any other species that
appears on both side of the equation. Check to see that both atoms and charge balance and
that the coefficients are reduced to simplest whole number.

Worked example
Let’s look at the reaction of aqueous potassium dichromate (K 2Cr2O7) with aqueous sodium chloride
to see how this method works. The reaction occurs in acidic solution according to the unbalanced
equation:
1

2 The first step is to decide which atoms have been oxidized and which have been reduced. In
the present case, the chloride atom is oxidized (from -1 to 0), and the chromium atom is reduced
(from +6 to +3). Thus, we can write two unbalanced half-reactions that show the separate steps:

Oxidation half-reaction

Reduction half-reaction

3 With the two half-reactions identified, each is balanced separately. Begin by balancing for all
atoms other than H and O. The oxidation half- reaction needs a coefficient of 2 before the Cl -, and the
reduction half-reaction needs a coefficient of 2 before the Cr3+.

Oxidation

Reduction

4 Next, balance both half-reactions for oxygen by adding H 2O to the side with less O, and

15
balance for hydrogen by adding H+ to the side with less H. The oxidation half-reaction has no H or O,
but the reduction reaction needs 7H 2O on the product side to balance for O and 14H + on the reactant
side to balance for H:

Oxidation

Reduction

5 Now, balance both half-reactions for charge by adding electrons (e -) to the side with the
greater positive charge. The oxidation half-reaction must have 2 e -added to the product side, and the
reduction half-reaction must have 6 e- added to the reactant side:

Oxidation

Reduction

With both half =-reactions now balanced, we need to multiply by suitable coefficient so that the
number of electrons released in the oxidation half-reaction is the same as the number consumed in the
reduction half-reaction. Since the reduction half-reaction has 6 e - but oxidation half-reaction has only
2 e-, the entire oxidation half-reaction must be multiplied by 3.

Oxidation

Reduction

6 Adding the two half-reactions together, and canceling the species that occur on both sides

16
(only electrons in this example), then gives the final balanced equation. Check the answer to make
sure it is balanced both for atoms and for charges

Charge: (-2)+(+14)+(6x-1)=+6 Charge: (2x+3)=+6

Study questions

1 Assign the oxidation numbers of the underlined elements

a) ClO3- b) SO32- c) Mn2O7 d) OsO4

2 Balance the following equations:

4 ATOMIC STRUCTURE
4.1 Fundamental particles
These are the basic building blocks of all atoms. Atoms, and hence all matter, consist
principally of three fundamental particles: electrons, protons, and neutrons. The mass of an
electron is very small compared with the mass of either a proton or a neutron. The charge on
a proton is equal in magnitude, but opposite in sign, to the charge on an electron.
Particle Mass Relative charge Location
electron 0.00054858 amu -1 Outside the nucleus
proton 1.00727647 amu +1 Within the nucleus
neutron 1.008665 amu 0 Within the nucleus

Since the protons and neutrons are located in the nucleus of an atom, they are collectively
called nucleons. The number of protons in the nucleus of an atom determines its identity; this
number is known as the atomic number of that element. For every element, the number of
protons is the same in all its atoms. The mass number of an atom is the sum of the number
of protons and the number of neutrons in its nucleus. For a neutral atom, the number of
electrons is equal to the number of protons.

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When atoms form ions, they either gain or lose electrons so it is possible to have two or more
species having same number of electrons, so we call them isoelectronic. For instance, Ne
(neon) atom, Mg 2+¿¿ , Na+¿¿, O2−¿¿ and F−¿¿ all have 10 electrons therefore, they are
isoelectronic.
A nuclide is an atom characterized by the constituents of its nucleus, that is, number of
protons and neutrons and it takes the form AZ X where X is the chemical symbol of element, A
is the mass number and Z is the atomic number. For instance, 168O is for oxygen atom with
mass number 16 and atomic number 8, it has 8 protons and 8 (16-8) neutrons since no charge
is indicated, then the number of electrons is also 8 electrons.
Most elements consist of atoms of different masses, called isotopes. The isotopes of a given
element contain the same number of protons (and also the same number of electrons) because
they are atoms of the same element. They differ in mass because they contain different
numbers of neutrons in their nuclei.
Isotopes are atoms of the same element containing the same number of protons but different
numbers of neutrons. A common example is 35 37
17 Cl and 17 Cl both are isotopes of chlorine: each

has 17 protons but with 18 and 20 neutrons respectively.

Many elements exist as two or more stable isotopes, although one isotope is usually present
in far greater abundance. For example, there are two stable isotopes of carbon, 13C and 12C, of
which 12C is the more abundant, constituting 98.89% of all carbon. Similarly, there are two
stable isotopes of nitrogen, 14N and 15N, of which 14N makes up 99.63% of all nitrogen
The average atomic mass of an element is the sum of the masses of its isotopes, each
multiplied by its natural abundance (the decimal associated with percent of atoms of that
element that are of a given isotope).
Exercise: The atomic weight of gallium is 69.72 amu. The masses of the naturally occurring
isotopes are 68.9257 amu gallium-69 and 70.9249 amu gallium-71. Calculate the percent
abundance of each isotope.

4.2 Atomic Models/ Development of Atomic Theory

The present atomic model has undergone changes over time as various scientific discoveries
were made. For this case, we shall look into four different atomic theories: Dalton’s,
Thompson’s, Rutherford’s and Bohr’s.
4.2.1 Dalton atomic theory
From 1803 to 1808, John Dalton, an English schoolteacher, used the two fundamental laws
of
chemical combination just described as the basis of an atomic theory. His theory involved

18
three
assumptions:
1. Each chemical element is composed of minute, indivisible particles called atoms. Atoms
can be neither created nor destroyed during a chemical change.
2. All atoms of an element are alike in mass (weight) and other properties, but the atoms of
one element are different from those of all other elements.
3. In each of their compounds, different elements combine in a simple numerical ratio, for
example, one atom of A to one of B (AB), or one atom of A to two of B (AB2)

4.2.2 J. J. Thomson atomic theory

Thomson knew that atoms had an overall neutral charge which implied that a source of
positive charge is needed to offset the negative charge on the electrons within the atom. As
such, Thomson proposed that atoms consist of negative particles floating within a soup of
diffuse positive charge. Due to this, the theory is also called the plum pudding model
The Thomson model of the atom stipulates that an atom consists of a uniform sphere of
positive charge with negative electrons embedded in the sphere

Reading: Cathode ray experiment

4.2.3 Rutherford atomic theory

Rutherford's atomic model became known as the nuclear model. In the nuclear atom, the
protons and neutrons, which comprise nearly all of the mass of the atom, are located in the
nucleus at the center of the atom. The electrons are distributed around the nucleus and
occupy most of the volume of the atom.

Atoms consist of very small, very dense positively charged nuclei surrounded by clouds of
electrons at relatively great distances from the nuclei.
In 1909, Rutherford, with his assistant Hans Geiger, began a line of research Using α
particles as probes to study the inner structure of atoms. Based on Thomson’s plum-pudding
model, Rutherford expected that most particles in a beam of particles would pass through
thin sections of matter largely undeflected, but that some α particles would be slightly
scattered or deflected as they encountered electrons. By studying these scattering patterns, he
hoped to deduce something about the distribution of electrons in atoms. Alpha particles were
detected by the flashes of light they produced when they struck a zinc sulfide screen placed

19
around gold foil. When Geiger and Ernst Marsden, a student, bombarded very thin foils of
gold with α particles, they observed the following:
 Most of the α-particles passed through without deflection, thus most space is empty.
 Some were deflected by small angle hence the positive charge in the atom is not
uniformly distributed. The positive charge is concentrated in small volume.
 Very few α particles were deflected back thus the volume occupied by the positively
charged particles in an atom is very small as compared to total volume.
Based on the observations;
 The small volume or positively charged region- He called the nucleus.
 Negative charges surrounding the nucleus revolve around the nucleus in a high speed in
circular paths called orbits.
 Negatively charged electrons and positively charged nucleus are held by electrostatic
forces.
 The size of the nucleus is smaller than the atom.
Limitations of Rutherford Model
 The motion of the electrons in the Rutherford model was unstable since any charged
particle moving on a curved path emits electromagnetic radiation. The electrons would
lose energy and spiral into the nucleus.
 It is based on future developments in the world of quantum mechanics.
 Did not say anything about the arrangement of electrons in an atom.

4.3 Electromagnetic Radiation

Electromagnetic radiation is a form of energy propagation where photons with both particle
and wave like properties travel at the speed of light.

Figure 1:Electromagnetic Spectrum

Electromagnetic radiation consists of packets (quanta) of oscillating electric and magnetic
fields which are perpendicular to one another and travelling in the form of harmonic wave.
Harmonic wave is characterized by properties such as frequency (v), wavelength (λ) and
wave number (v-1). Frequency (v), it is the number of waves passing a point in unit time
while wavelength (λ) distance between two successive crest or troughs.

20
The relationship between the wavelength and frequency of electromagnetic radiation, with c
is
λv=c
In a vacuum, the speed of electromagnetic radiation, c, is the same for all wavelengths,
2.99792458 x 108 m/s which is approx. 3×108 m/s.
Wavenumber (λ-1) is the of reciprocal of wavelength. Units for (λ -1) is m-1 in most cases
reported as cm-1
1 v
=
λ c
Exercise: A green line of wavelength 4.86 x10-7 m is observed in the emission spectrum of
hydrogen. Calculate the energy of this green light in kJ/mol.

The packets of electromagnetic radiation are known as quanta or photons. Each photon has
energy, E, given by:
E=hv
-34
Where h is Planck’s constant =6.6262x10 Js

4.4 Photoelectric Effect

The photoelectric effect is a phenomenon that occurs when light shined onto a metal surface
causes the ejection of electrons from that metal. The electrons that are ejected from the metal
are called photoelectrons
It was observed that only certain frequencies of light are able to cause the ejection of
electrons. If the frequency of the incident light is too low (red light, for example), then no
electrons were ejected even if the intensity of the light was very high or it was shone onto the
surface for a long time.
If the frequency of the light was higher (green light, for example), then electrons were able to
be ejected from the metal surface even if the intensity of the light was very low or it was
shone for only a short time. This minimum frequency needed to cause electron ejection is
referred to as the threshold frequency. The energy of radiation corresponding to this
frequency is called the work function.
During photoemission, one photon only interacts with one electron, which is why if the
frequency of the electron is below the threshold frequency then no electron is ejected no
matter the intensity of time of exposure. Also, increasing the intensity only increases the
number of photons thus translates to more electrons being ejected. If the frequency of the
incident photon is increased beyond the threshold frequency, then the extra energy is of the
photon is converted to kinetic energy as the photoelectron gains motions
Energy of photon=work function + Kinetic energy Which gives
1 2
hv=ϕ+ mV
2
where h is Planck’s constant, v is frequency, ϕ is work function, m is mass of photoelectron
and V is velocity of ejected photoelectron
Exercise: The work function of copper metal is ϕ=7.53 x -19. If we shine light with a

21
frequency of 3.0 x 10 16 Hz on the copper metal.
a) Will the photoelectric effect be observed?
b) If photoelectrons are emitted, what is their velocity?

4.5 Atomic Spectra/Hydrogen Spectra

When an electric current is passed through a gas in a vacuum tube at very low pressures,
however, the light that the gas emits can be dispersed by a prism into distinct lines. The lines
can be recorded photographically, and the wavelength of light that produced each line can be
calculated from the position of that line on the photograph.
Similarly, we can shine a beam of white light (containing a continuous distribution of
wavelengths) through a gas and analyze the beam that emerges. We find that only certain
wavelengths have been absorbed.
The wavelengths that are absorbed in this absorption spectrum are also given off in the
emission experiment. Each spectral line corresponds to a specific wavelength of light and
thus to a specific amount of energy that is either absorbed or emitted.
An atom of each element displays its own characteristic set of lines in its emission or
absorption spectrum.

Figure 2: Spectra lines in the hydrogen atom

All lines in all the series obey the general expression given in equation above where n > m.
For the Lyman series, n > 1, for the Balmer series, n >2, and for the Paschen, Brackett and
Pfund series, n > 3, 4 and 5 respectively.
Balmer and Rydberg showed that the wavelengths of the various lines in the hydrogen
spectrum can be related by a mathematical equation

7 -1
1
λ ( 1 1
=R 2 − 2
m n )
where R is 1.097 x 10 m and is known as the Rydberg constant. The n’s are positive
integers, and n is greater than m (n>m)
The equation can be applied to any other element by factoring in the atomic number (Z) of
the element

22
 1
λ
=R Z
2 1
(2
m n
1
)
− 2 Exercise:

1. Calculate the frequency and wavelength of emitted photon when an electron drops from
n=5 to n=2 level in hydrogen atom.

4.6 Bohr Atomic model

Following the discoveries of hydrogen emission spectra and the photoelectric effect, Niels
Bohr proposed a new model of the atom in 1915. To remedy the stability problem of the
Rutherford atomic model, Bohr proposed that electrons do not radiate energy as they orbit
the nucleus, but exist in states of constant energy which he called stationary states. His theory
became knowns as the planetary model
Therefore, the key postulates of Bohr’s atomic theory are:
a) Electrons revolve around the nucleus in a fixed circular path termed “orbits” or “shells”
or “energy level.” The orbits are termed as “stationary orbit.”
b) Every circular orbit will have a certain amount of fixed energy and these circular orbits
were termed orbital shells. The electrons will not radiate energy as long as they continue
to revolve around the nucleus in the fixed orbital shells.
c) The different energy levels are denoted by integers such as n=1 or n=2 or n=3 and so on.
These are called as quantum numbers. The range of quantum number may vary and begin
from the lowest energy level (nucleus side n=1) to highest energy level
d) The different energy levels or orbits are represented in two ways such as 1, 2, 3, 4… or
K, L, M, N….. shells. The lowest energy level of the electron is called the ground state.
e) The change in energy occurs when the electrons jump from one energy level to other. In
an atom, the electrons move from lower to higher energy level by acquiring the required
energy. However, when an electron loses energy it moves from higher to lower energy
level.

If we apply the Bohr model to the H atom, the radius of each allowed circular orbit can be
determined from equation below. The origin of this expression lies in the centrifugal force
acting on the electron as it moves in its circular orbit; for the orbit to be maintained, the
centrifugal force must equal the force of attraction between the negatively charged electron
and the positively charged nucleus.
2 4
Z me
2 2
∗1 2
8 h ε° −18 Z
En = =−2.18 x 10 J
n2 n2
or

23
 2 4
Z me
2 2
∗1 2
8 h ε° Z
En = =−13.6 eV
n2 n2
Where, m- mass of electron 9.1079x10-31 kg
e- electronic charge 1.602x10-19 C
h-Planck’s constant 6.626x10-34 Js
ε °- permittivity of free space 8.854188x10-12 C2s2kg-1m-3
Z- nuclear charge

∆ E=En 2−E n 1

∆ E=−2.18 x 10
−18
Z
2
( 1 1
2
− 2 J
n 1 n2 )
∆ E=−13.6 Z
2
( 1 1
2
− 2 eV
n 1 n2 )
Bohr Radius Derived
Bohr proposed that the angular momentum, L, of an electron in its orbit is quantized (only
specific discrete values are allowed) given by
h
L=n
2π
Where n takes the values 1, 2, 3, ….
The since an electron is in a circular motion in the orbits, the angular momentum of the
electron whose mass is me in an orbit with a radius r n , at a velocity v , will be given by
L=me v r n

Equating the two expression for the angular momentum we have

nh
m e v r n=
2π
Making v the subject of the formula, we have
nh
v=
2 π me r n

For an electron to follow a circular path, then we have a centripetal force and a coulomb force
involved
For an electron of mass, me , moving in an orbit of radius r n , at a velocity of v , the centripetal
force is given by
2
me v
F ce =
rn

24
Considering the electron with a charge of q e , moving around the nucleus of atomic number Z
and the charge of each proton is q e separated by a distance of r n . The Coulomb force on the
electron will be given by
K ( Zq e )( qe )
F co= 2
rn

Considering that the nucleus is massive it will be stationary and the electrons will be moving
around it, therefore, the centripetal force will be equal to the Coulomb force
K ( Zq e ) ( q e ) me v 2
2
=
rn rn

nh
Substituting for v= we get
2 π me r n

( )
2
nh
2
me
K Z qe 2 π me r n
2
=
rn rn

Re-arranging the equation

2 2 2
K Z qe n h
2
=me 2 2 3
rn 4 π me r n

The equation simplifies

2 2
2 n h
K Z qe = 2
4 π me r n

Re-arranging to make the radius the subject of the formula, we have

2 2
nh
rn = 2 2
4 π me K Z q e

Since the only variable in the equation will be n, then, the equation can be reduced to
2
r n =n ao

Where n is a positive integer, n=1, 2, 3, … and a o is a constant known as Bohr radius

( ao=5.292×10−11 m )
Similarly, the energy associated with any circular orbit is given by
−18
2.18 × 10 J
En = 2
n
Therefore, the energy for n=1, n=2 and n=7 are
−18
−2.18 ×10 J −18
E 1= 2
=−2.18 × 10 J
1

25
 −18
−2.18 ×10 J −19
E 2= 2
=−5.45 × 10 J
2
−18
−2.18 × 10 J −20
E7 = 2
=−4.45 ×10 J
7
Electron jumping from the second energy level to the seventh energy level, will have the
energy absorbed given as

E2− E7=5.45 ×10−19 J− ( 4.45 ×10−20 J ) =5.01× 10−19 J

Since electrons can jump from one energy level to another, the energy associated with such a
hydrogen transition in a hydrogen atom will be the energy difference between the two energy
levels. For instance, in a transition between n1 and n2 , the energy of each level will be
−18 −18
2.18 ×10 J 2.18 ×10 J
En = 2 and nE = 2
1
n1 n2 2

Therefore, the difference in energy between the two energy levels will be
−18 −18
2.18 ×10 J 2.18 × 10 J
∆ E=En −En = 2
− 2
1
n1 2
n2

Which simplifies to

E=2.18 ×10
−18
J
( 1
2
1
− 2
n1 n 2 )
For instance, a jump between the second and seventh energy levels will be calculated as

E=2.18 ×10
−18
J
( 21 − 71 )=2.18 ×10
2 2
−18
J ( 0.22959 )=5.01 ×10
−19

Exercise: When an electron undergoes transition from n=2 to n=7, to find the a) wavelength
(nm), frequency, quantum energy (R = 1.097 ×10 7 m−1)

1
λ
1 1
( )
=R 2 − 2 Substitute the values given
n 1 n2

1
λ
7 −1 1
=1.097 ×10 m 2
2 7 (
1
)
7 −1 6 −1
− 2 =1.097 × 10 m ×0.22959=2.5186 ×10 m

1 −7
¿ 6 −1
=3.97 ×10 m
2.5186 ×10 m
Convert to nm
9
−7 10 nm
λ=3.97 ×10 m× =397 nm
1m
Frequency

26
 8
c 3.00× 10 m/s 14
v= = =7.556× 10 Hz
λ 3.97 ×10−7 m

Quantum energy
−34 14 23 −1
E=hv N A=6.626 × 10 Js ×7.556 ×10 Hz ×6.022 ×10 mol =301,492 J /mol

Convert to kJ/mol
E = 301.492 kJ/mol
Similarly, the energy associated with any circular orbit is given by
−18
2.18 × 10 J
En = 2
n
Therefore, the energy for n=1, n=2 and n=7 are
−18
−2.18 ×10 J −18
E 1= 2
=−2.18 × 10 J
1
−18
−2.18 ×10 J −19
E 2= 2
=−5.45 × 10 J
2
−18
−2.18 × 10 J −20
E7 = 2
=−4.45 ×10 J
7
Electron jumping from the second energy level to the seventh energy level, will have the
energy absorbed given as

E2− E7=5.45 ×10−19 J− ( 4.45 ×10−20 J ) =5.01× 10−19 J

Since electrons can jump from one energy level to another, the energy associated with such a
hydrogen transition in a hydrogen atom will be the energy difference between the two energy
levels. For instance, in a transition between n1 and n2 , the energy of each level will be
−18
2.18 ×10 J
En = 2
1
n1
−18
2.18 ×10 J
En = 2
2
n2

Therefore, the difference in energy between the two energy levels will be
−18 −18
2.18 ×10 J 2.18 × 10 J
∆ E=En −En = 2
− 2
1 2
n1 n2

Which simplifies to

E=2.18 ×10
−18
J
( 1
2
1
− 2
n1 n 2 )
For instance, a jump between the second and seventh energy levels will be calculated as

27
 E=2.18 ×10
−18
J
( 1 1
2
2 7 ) −18
− 2 =2.18 ×10 J ( 0.22959 )=5.01 ×10
−19

N=2 to n=7, to find the a) wavelength (nm), frequency, quantum energy (R = 1.097 ×10 7 m−1

1
λ
1
(
1
)
=R 2 − 2 Substitute the values given
n 1 n2

1
λ
7 −1 1
=1.097 ×10 m 2(
2 7
1
)7 −1 6 −1
− 2 =1.097 × 10 m ×0.22959=2.5186 ×10 m

1 −7
¿ 6 −1
=3.97 ×10 m
2.5186 ×10 m
Convert to nm
9
−7 10 nm
λ=3.97 ×10 m× =397 nm
1m
Frequency
8
c 3.00× 10 m/s 14
v= = −7
=7.556× 10 Hz
λ 3.97 ×10 m

Quantum energy
−34 14 23 −1
E=hv N A=6.626 × 10 Js ×7.556 ×10 Hz ×6.022 ×10 mol =301,492 J /mol

Convert to kJ/mol
E = 301.492 kJ/mol

Failures of the Bohr Model

 Fails to provide any understanding why some spectral lines are brighter than others.
 There is no mechanism for the calculation of transition probability.
 The model treats electrons as if they were miniature planet with definite radius and
momentum. This is against the Heisenberg uncertainty principle which dictates that
position and momentum cannot be simultaneously determined.

4.7 The Wave Nature of the Electron

Einstein’s idea that light can exhibit both wave properties and particle properties suggested to
Louis de Broglie that very small particles, such as electrons, might also display wave
properties under the proper circumstances. In 1925 de Broglie predicted that a particle with a
mass m and velocity v should have the wavelength associated with it.
h
The numerical value of this de Broglie wavelength is given by λ= (where h = Planck’s
mv
constant)
De Broglie first used Einstein's famous equation relating matter and energy:
2
E=mc ..............1
E = energy, m = mass, c= speed of light

28
Using Planck's theory which states every quantum of a wave has a discrete amount of energy
given by Planck's equation:
c
E=h ν=h .............2
λ
E = energy, h = Plank's constant (6.62607 x 10-34 J s), ν= frequency, λ=wavelength, c= speed
of light.
Because real particles do not travel at the speed of light, De Broglie submitted velocity ( v) for
the speed of light (c).
2 v
mv =h
λ
h
mv=
λ
h h
λ= =
mv p
a) Calculate the wavelength in meters of an electron traveling at 1.24 x 107 m/s. The
mass of an electron is 9.11 x 10 -28 g.
b) Calculate the wavelength of a baseball of mass 0.148835 kg traveling at 92.5 mph.

One of the underlying principles of quantum mechanics is that we cannot determine precisely
the paths that electrons follow as they move about atomic nuclei. The Heisenberg
Uncertainty Principle states that it is impossible to determine accurately both the
momentum and the position of an electron (or any other very small particle) simultaneously
Some basic ideas of quantum mechanics are:
When atoms or molecules emit or absorb radiation (light), they change their energies. The
energy change in the atom or molecule is related to the frequency or wavelength of the light
hc
emitted or absorbed by the equations: E=hv or E=
λ
Atoms and molecules can exist only in certain energy states. In each energy state, the atom or
molecule has a definite energy. When an atom or molecule changes its energy state, it must
emit or absorb just enough energy to bring it to the new energy state (the quantum condition).
Atoms and molecules possess various forms of energy. Let us focus our attention on their
electronic energies.
This gives a relationship between the energy change, ∆E, and the wavelength, λ, of the
radiation emitted or absorbed. The energy lost (or gained) by an atom as it goes from higher
to lower (or lower to higher) energy states is equal to the energy of the photon emitted (or
absorbed) during the transition.
The allowed energy states of atoms and molecules can be described by sets of numbers called
quantum numbers.

4.8 Compton Effect

In this phenomenon a particle of light collides with a stationery electron acquires some kinetic energy
and moves in certain direction and also another particle of light is produced.
We can think of the photon as losing an amount of energy in the collision that is the same as the
kinetic energy (KE) gained by the electron, although actually separate photons are involved. If the
initial photon has the frequency ν associated with it, the scattered photon has the lower frequency ν′,
where;
Loss in photon energy = gain in electron energy

29
hν−hν′=KE
and the momentum of a massless particle is related to its energy by the formula
E=pc
since the energy of a photon is E, its momentum is
E hv
p= =
c c
Momentum, unlike energy is a vector quantity that incorporates direction as well as magnitude, and in
the collision momentum must be conserved in each of two mutually perpendicular directions.

4.9 Pair Production

In these phenomena light of relatively high energy passes near a large nucleus eg gold and in the
0 0
process that light is converted into 2 particles. These particles are −1e and +1e . However, immediately
after they are converted into 2 photons of lower frequency.
0 0
A photon of high energy → −1e + +1 e → 2 photons of lower frequency.
This supports the particle wave duality of light.

4.10 The Schrödinger’s Model of the Atom

It is considered to be the modern theory of the atom and was proposed by Schrödinger in 1925. The
model was based on modern physics as opposed to the classical physics. One branch of modern
physics is the quantum mechanics.
Difference between classical and modern physics
Measurements in modern physics is relative or probability while classical physics is accuracy limited.
One of the aspects of modern physics/quantum mechanics is the use of quantity called wavefunction
during measurements (Ψ).
Wavefunction Ψ- Has no physical meaning but it is absolute magnitude.
2
|ψ| =√ ωav ⅇfunctⅈon
2
|ψ| =probability
If you are looking for a particle in a box or an electron in an atom there are two possibilities
2
|ψ| =0 The particle does not exist in the box.
2
|ψ| =1.0 The particle is somewhere in the box
However, the Ψ must meet certain conditions (boundary conditions) for it to have meaningful
solutions to the Schrödinger wave equation (SWE).
The following is a summary of the conditions;
i) the wavefunction must be finite (continuous)
+∞

∫ |Ψ | ⅆx =0 The particle does not exist in the box.

2
In summary
−∞
+∞

∫ |Ψ | ⅆx =1.0 The particle is somewhere in the box

2
Or
−∞
The above process is known as the normalization of the wave ie making sure that the wave is finite.
ii) the wavefunction bust be single value.
The Ψ can only have one value at any particular point (x,y,z) and at any particular time.
iii) the wave function and its derivatives must be continuous like a normal wave.
Ψ, we can obtain the derivatives;
ⅆ ψ ⅆψ ⅆψ
The 1st derivatives , ∧¿
ⅆ x ⅆy ⅆz
2 2
nd ⅆ Ψ ⅆ Ψ ⅆ2 Ψ
The 2 derivatives , and
ⅆ x2 ⅆ y2 ⅆ z2
In the process of determining the presence of a particle at point x,y,z and at time t secs, two quantities
are very important which are;
The particle position as given by the cartesian coordinates x,y,z.

30
The particle momentum (vector quantity) given by mv, where m is mass of particle/electron and v is
the velocity.
Another aspect of the quantum mechanics is the presence of the Heisenberg uncertainty principle.
The following is the SWE in cartesian coordinates;
ⅆ 2 Ψ ⅆ 2 Ψ ⅆ2 Ψ 8 π 2 m (
+ + + 2 E−V ) Ψ =0
ⅆ x2 ⅆ y2 ⅆ z2 h
Where;
Ψ - wavefunction
h- Planck’s constant
m- mass of electron
E- total energy
V- potential energy of the
particle
x,y,z- cartesian coordinates

31
Having solved the wave equation, what are the results?
i. The wavefunction ψ is a solution of the Schrȍdinger equation and describes the behaviour
of an electron in a region of space called the atomic orbital.
ii. We can find energy values that are associated with particular wavefunctions.
iii. The quantization of energy levels arises naturally from the Schrȍdinger equation

An atomic orbital is defined as the boundary surface encloses 95% of the electron density for a
particular wavefunction Ψ. Each atomic orbital (Ψ) may be uniquely defined by a set of four quantum
numbers.
The above equation is only applicable for H atom, and ions that are H like such as He + and Li+. Ions
and atoms with more than one electron require a more complicated equation than the above.
Therefore, the above cartesian coordinates equation can be converted to a spherical polar coordinates
radial (r), zenith angle (θ), atimuth angle (ϕ).

Separation of variables
The above SWE in spherical can be divided into 3 partial wave equations where each part represents
the respective polar coordinates e.g
Radial partial wave equation- describes how the Ψ varies with radius r with zenith and atimuth angle
kept constant.
Zenith partial wave equation- shows how the Ψ varies with zenith angle (θ) while the rest are kept
constant.
Atimuth partial wave equation- shows how Ψ varies with atimuth angle while the rest are kept
constant.

4.11 Electronic Structure of the Atom

4.11.1 Quantum Numbers
There are various states available to a single electron. Each of these possible states is
described by four quantum numbers. We can use these quantum numbers to designate the
electronic arrangements in all atoms, their so- called electron configurations.
These quantum numbers play important roles in describing the energy levels of electrons and
the shapes of the orbitals that describe distributions of electrons in space.
An atomic orbital is a region of space in which the probability of finding an electron is high.
The four quantum numbers are:
a) The principal quantum number, n, describes the main energy level, or shell, an
electron occupies. It may be any positive integer: n = 1, 2, 3, 4, . . .
b) The angular momentum quantum number, l, designates the shape of the region in
space that an electron occupies. Within a shell (defined by the value of n, the principal
quantum number) different sublevels or subshells are possible, each with a characteristic
shape. The angular momentum quantum number designates a sublevel, or specific shape
of atomic orbital that an electron may occupy.
This number, l, may take integral values from 0 up to and including (n - 1): 0, 1, 2, . . ., (n -
1)
Thus, the maximum value of l is (n - 1). We give a letter notation to each value of l. Each
letter corresponds to a different sublevel (subshell).

32
l = 0, 1, 2, 3, . . ., (n - 1) corresponds s, p, d, f
In the first shell, the maximum value of l is zero, which tells us that there is only an s
subshell and no p subshell.
In the second shell, the permissible values of l are 0 and 1, which tells us that there are only s
and p subshells.
c) The magnetic quantum number, ml, designates the specific orbital within a subshell.
Orbitals within a given subshell differ in their orientations in space, but not in their
energies. Within each subshell, ml may take any integral values from -l through zero up
to and including +l.
ml = -l, . . ., 0, . . ., +l
The maximum value of ml depends on the value of l. For example, when l= 1, which
designates the p subshell, there are three permissible values of ml: -1, 0, and +1. Thus, three
distinct regions of space, called atomic orbitals, are associated with a p subshell. We refer to
these orbitals as the px, py, and pz orbitals.
d) The spin quantum number, ms, refers to the spin of an electron and the orientation of
the magnetic field produced by this spin. For every set of n, l, and ml values, ms can take
the value - ½ or + ½
The values of n, l, and ml describe a particular atomic orbital. Each atomic orbital can
accommodate no more than two electrons, one with ms – ½ and another with ms = + ½

4.12 Atomic Orbitals

For each neutral atom, we must account for a number of electrons equal to the number of
protons in the nucleus, that is, the atomic number of the atom. Each electron is said to occupy
an atomic orbital defined by a set of quantum numbers n, l, and ml.
In any atom, each orbital can hold a maximum of two electrons. Within each atom, these
atomic orbitals, taken together, can be represented as a diffuse cloud of electrons.
The main shell of each atomic orbital in an atom is indicated by the principal quantum
number n. The value n = 1 describes the first, or innermost, shell. These shells have been

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referred to as electron energy levels. Successive shells are at increasingly greater distances
from the nucleus. For example, the n = 2 shell is farther from the nucleus than the n = 1 shell.
The electron capacity of each shell is given by 2n2.
Each shell has an s subshell (defined by l =0) consisting of one s atomic orbital (defined by
m = 0). We distinguish among orbitals in different principal shells (main energy levels) by
using the principal quantum number as a coefficient; 1s indicates the s orbital in the first
shell, 2s is the s orbital in the second shell, 2p is a p orbital in the second shell, and so on
The shape of an s orbital is as shown below

Beginning with the second shell, each shell also contains a p subshell, defined by l = 1. Each
of these subshells consists of a set of three p atomic orbitals, corresponding to the three
allowed values of ml (-1, 0, and +1) when l = 1. The sets are referred to as 2p, 3p, 4p, 5p, . . .
orbitals to indicate the main shells in which they are found. Each set of atomic p orbitals
resembles three mutually perpendicular equal-arm dumbbells as shown below.

Beginning at the third shell, each shell also contains a third subshell (l = 2) composed of a set
of five d atomic orbitals (ml = -2, -1, 0, +1, +2). They are designated 3d, 4d, 5d, . . . to
indicate the shell in which they are found.
In each of the fourth and larger shells, there is also a fourth subshell, containing a set of
seven f atomic orbitals (ml = -3, -2, -1, 0, +1, +2, +3).
Thus, we see the first shell contains only the 1s orbital; the second shell contains the 2s and
three 2p orbitals; the third shell contains the 3s, three 3p, and five 3d orbitals; and the fourth
shell consists of a 4s, three 4p, five 4d, and seven 4f orbitals. All subsequent shells contain s,
p, d, and f subshells as well as others that are not occupied in any presently known elements
in their lowest energy states.

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 Elect
rons are negatively charged, and they behave as though they were spinning about axes
through their centers, so they act like tiny magnets. The motions of electrons produce
magnetic fields, and these can interact with one another. Two electrons in the same orbital
having opposite ms values are said to be spin-paired, or simply paired. ms has two possible
values, - ½ and + ½ for each atomic orbital

4.13 Electron Configuration

Each electron is described by the same allowed combinations of quantum numbers (n, l, m l,
and ms). The electronic arrangement for each atom is called the ground state electron
configuration. In describing ground state electron configuration, the guiding idea is that the
total energy of the atom is as low as possible.
Aufbau Principle: Each atom is “built up” by:
a. adding the appropriate numbers of protons and neutrons as specified by the atomic
number and the mass number, and
b. adding the necessary number of electrons into orbitals in the way that gives the lowest
total energy for the atom.
From the Aufbau principle we have the Aufbau diagram

Pauli Exclusion Principle: No two electrons in an atom may have identical sets of four
quantum numbers

Hund’s Rule: Electrons occupy all the orbitals of a given subshell singly before pairing
begins. These unpaired electrons have parallel spins

Methods of writing electronic configuration:

1) orbital diagrams (box notation): An orbital diagram, like those shown above, is a visual
way to reconstruct the electron configuration by showing each of the separate orbitals and
the spins on the electrons. This is done by first determining the subshell (s,p,d, or f) then

35
 drawing in each electron according to the stated rules above.

2) spdf notation: The most common way to describe electron configurations is to write
distributions in the spdf notation. Although the distributions of electrons in each orbital
are not as apparent as in the diagram, the total number of electrons in each energy level is
described by a superscript that follows the relating energy level. To write the electron
configuration of an atom, identify the energy level of interest and write the number of
electrons in the energy level as its superscript
1s22s22p63s23p1
3) Noble gas notation: The noble gases have the most stable electron configurations, and are
known for being relatively inert. All noble gases have their subshells filled and can be
used them as a shorthand way of writing electron configurations for subsequent atoms.
This method of writing configurations is called the noble gas notation, in which the noble
gas in the period above the element that is being analyzed is used to denote the subshells
that element has filled and after which the valence electrons are written

Paramagnetism and Diamagnetism

Substances that contain unpaired electrons are weakly attracted into magnetic fields and are
said to be paramagnetic. By contrast, those in which all electrons are paired are very weakly
repelled by magnetic fields and are called diamagnetic
Exercise: For the following elements, determine the electron configurations and
subsequently give the group and period, and determine whether they are diamagnetic or
paramagnetic:
a) magnesium, Mg (Z=12);
b) germanium, Ge (Z=32);
c) molybdenum, Mo (Z=42)
d) radon, Rn (Z=86)

5 THE PERIODIC TABLE

The Periodic Table of Elements categorizes like elements together. Dmitri Mendeleev, a
Russian scientist, was the first to create a widely accepted arrangement of the elements in
1869. Mendeleev believed that when the elements are arranged in order of increasing atomic
mass, certain sets of properties recur periodically.
The periodic table is a table of the chemical elements which are arranged by atomic number,
electron configuration, and recurring chemical properties. The periodic table consists of
periods and groups.

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A group is a vertical column in the periodic table; also called a family while a period is a
horizontal row in the periodic table. The current periodic table consists of 7 periods and 18
groups.
The periodic table can be divided into two categories: “A” and “B” groups. The A groups
contain elements in which s and p orbitals are being filled. Elements within any particular A
group have similar electron configurations and chemical properties. The B groups are those
in which there are one or two electrons in the s orbital of the outermost occupied shell, and
the d orbitals, one shell smaller, are being filled.

These trends explain the periodicity observed in the elemental properties of atomic radius,
ionization energy, electron affinity, and electronegativity.
1 Elements are arranged with increasing atomic number in rows (called periods) and
columns (called groups).
2 Elements in Groups 1 and 2 are also called s block elements: valence electrons fill
in s orbitals.
3 Elements in Groups 13 to 18 are also called p block elements: valence electrons
fill in p orbitals.
4 Elements in Groups 1, 2 and 13 - 18 are called main group elements.
5 Elements in Groups 3 - 11 are called transition metal because they have partially
filled d orbitals. Elements in Groups 3 - 12 are called d block elements because
valence electrons filled in d orbitals.
6 f block elements (also called Lanthanides and Actinides): valence electrons filling

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 in f orbitals.
7 Elements in each group have similar valence-electron (electrons in the outermost
shell) configuration and therefore similar properties.

The electron configurations of the A group elements and the noble gases can be predicted
reliably. However, there are some more pronounced irregularities in the B groups below the
fourth period
Group IA - a single electron in their outermost shell - ns1
Group IIA - 2 electrons in their outermost shell - ns2
Group IIIA - 3 electrons in their outermost shell - ns2np1
Group IVA – 4 electrons in the outermost shell - ns2np2
Group VA – 5 electrons in the outermost shell - ns2np3
Group VIA – 6 electrons in the outermost shell - ns2np4
Group VIIA – 7 electrons in the outermost shell - ns2np5
Group VIIIA – 8 electrons in the outermost shell - ns2np6

The fundamental basis of the periodic table is that it reflects similarities and trends in
electron configurations. It is easy to use the periodic table to determine many important
aspects of electron configurations of atoms. The many trends in chemical and physical
properties that we correlate with the periodic table are ultimately based on the trends in
electron configurations.
The A and B designations for groups of elements in the periodic table are somewhat
arbitrary, and they are reversed in some periodic tables. In another designation, the groups
are numbered 1 through 18.
Elements with the same group numbers, but with different letters, have relatively few similar
properties. The origin of the A and B designations is the fact that some compounds of
elements with the same group numbers have similar formulas but quite different properties,
for example, NaCl (IA) and AgCl (IB), MgCl 2 (IIA) and ZnCl2 (IIB). Variations in the
properties of the B groups across a row are not nearly as regular and dramatic as the
variations observed across a row of A group elements.
The outermost electrons have the greatest influence on the properties of elements. Adding an
electron to an inner d orbital results in less striking changes in properties than adding an
electron to an outer s or p orbital.
Many physical properties, such as melting points, boiling points, and atomic volumes, show

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periodic variations. The variations in these properties depend on electron configurations,
especially the configurations in the outermost occupied shell, and on how far away that shell
is from the nucleus

5.1 Periodic Properties of Elements

The properties of the elements are periodic functions of their atomic numbers. The outermost
electrons have the greatest influence on the properties of elements. Here we shall look into
the trend of properties across a period and down a group. Across a period, there is an increase
in number of valence electrons from left to right while down a group the number of valence
electrons are constant.

5.1.1 Nuclear charge and shielding

The number of protons in the nucleus of an atom affects the extent of attraction between the
nucleus and negatively charged electrons. Nuclear charge is a measure of the effect of the
number of protons in the nucleus and their ability to attract the negative electrons in orbits
around the nucleus.
The effective nuclear charge, Z eff, experienced by an electron in an outer shell is less than the
actual nuclear charge, Z. This is because the attraction of outer-shell electrons by the nucleus
is partly counterbalanced by the repulsion of these outer-shell electrons by electrons in inner
shells. We say that the electrons in inner shells screen, or shield, electrons in outer shells
from the full effect of the nuclear charge.
As you move across the period from left to right, the number of inner shells is constant,
therefore, the valence electrons experience a relatively constant shielding against an
increasing nuclear charge. Therefore, the effective nuclear charge will be increasing this
leading to the valence electrons being held tightly thus drawn closer to the nucleus.

5.1.2 Atomic size (Atomic radius)

Down a group, the atomic radii increase from top to bottom as electrons are added to shells
farther from the nucleus. As we move from left to right across a period in the periodic table,
atomic radii of representative elements decrease as a proton is added to the nucleus and an
electron is added to a particular shell.

5.1.3 Ionic radii

Ions are formed by either gain or loss of electrons by atoms. Metals lose electrons to form

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cations, and the radius of the cations will always be smaller than then corresponding neutral
atom since the loss of electron reduces the size of the electron cloud while the nuclear charge
remains constant. On the other hand, the radius of the anions will be larger than that of the
corresponding neutral atoms since the gained electron(s) increases the size of the electron
cloud.
Down the group, the ionic radii will always increase due to the increasing number of
occupied shells. Across a period, the size of the cations decreases since the number of
electrons are the same against an increasing nuclear attraction. For anions, across a period
there is a decreasing radius of the ions since the ions are isoelectronic but with an increasing
nuclear charge

5.1.4 Ionization energy

This is the minimum amount of energy required to remove the most loosely bound electron
from an isolated gaseous atom to form an ion with a positive charge. First ionization energy
(IE1) is the amount of energy required to remove the first electron to form a cation with +1
charge, the second ionization energy (IE 2) is the amount of energy required to remove the
second electron to form a cation with a +2 charge, and so forth.
For a given element, IE2 is always greater than IE 1 because it is always more difficult to
remove an electron from a positively charged ion than from the corresponding neutral atom.
Ionization energies measure how tightly electrons are bound to atoms. Ionization always
requires energy to remove an electron from the attractive force of the nucleus. Low
ionization energies indicate ease of removal of electrons, and hence ease of positive ion
(cation) formation.
As we move down the group, the first ionization energies become smaller. The force of
attraction of the positively charged nucleus for electrons decreases as the square of the
distance between them increases. So as atomic radii increase in a given group, first ionization
energies decrease because the outermost electrons are farther from the nucleus.
Effective nuclear charge increases going from left to right across a period. The increase in
effective nuclear charge causes the outermost electrons to be held more tightly, making them
harder to remove. The first ionization energies therefore generally increase from left to right
across the periodic table.
For any element, there is a sudden jump in successive ionization energy values when all the
valence electrons of that element have been removed. For instance, in Na atom the huge
jump is between IE1 and IE2, for Mg the huge jump is between IE 3 and IE2. This is because

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once the valence electrons have all been removed, the next electron is removed from an inner
core energy level that experiences increased effective shielding.
5.1.5 Electron affinity
The electron affinity (EA) of an element may be defined as the amount of energy absorbed
when an electron is added to an isolated gaseous atom to form an ion with a 1- charge. It is
the neutral atom's likelihood of gaining an electron
For many reasons, the variations in electron affinities are not regular across a period. The
general trend is: the electron affinities of the elements become more negative from left to
right in each period.
Metals like to lose valence electrons to form cations to have a fully stable octet. They absorb
energy (endothermic) to lose electrons. The electron affinity of metals is lower than that of
nonmetals.
Electron affinity decreases down the groups because the electrons are placed in a higher
energy level far from the nucleus, thus a decrease from its nuclear attraction as the shielding
effect increases

5.1.6 Electronegativity
The electronegativity (EN) of an element is a measure of the relative tendency of an atom to
attract electrons to itself when it is chemically combined with another atom. For the
representative elements, electronegativities usually increase from left to right across periods
and decrease from top to bottom within groups.
From left to right across a period of elements, electronegativity increases. If the valence shell
of an atom is less than half full, it requires less energy to lose an electron than to gain one.
Conversely, if the valence shell is more than half full, it is easier to pull an electron into the
valence shell than to donate one. From top to bottom down a group, electronegativity
decreases. This is because atomic number increases down a group, and thus there is an
increased distance between the valence electrons and nucleus, or a greater atomic radius.
There is an electronegativity scale that reflects how strong the bond energies for atoms are.
The scale is called the Pauling Scale and it assigns atoms electronegativity values between
0.7 and 3.98.

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