CHEM 115 Chemistry

Sedef Günday Özcan

Atomic Structure
 Before Dalton…
Law of Conservation of Mass (Antoine Lavoisier,1789)
• The total mass of the substances does not change during a
chemical rxn. The number of substance may change, but the total
amount of matter remains constant.
• “Matter cannot be created or destroyed” in chemical rxns.

16 X + 8Y 8 X2Y
Before Dalton…
Law of Conservation of Mass (Antoine Lavoisier,1789)

K2CrO4
Ag2CrO4 + KNO3

AgNO3

A beaker with a silver nitrate When the solutions are mixed,

solution and a graduated a chemical reaction occurs that
cylinder with a potassium forms silver chromate (red
chromate solution are placed precipitate) in a potassium
on a single-pan balance, which nitrate solution. Note that the
displays their combined mass total mass 104.50 g remains
104.50 g. unchanged.
Before Dalton…
Law of Definite Proportions (Joseph Proust, 1799)
(Law of Constant Composition)

• Different samples of the same compound always

contain its constituent elements in the same
proportion by mass.

Mass of element in compound

Mass of element in sample = Mass of compound in sample x
Mass of compound

Calcium carbonate is found naturally in many forms, including

marble (top), coral (bottom), chalk, and seashells. The mass
percents of its component elements do not change regardless of
the compound’s source.
 EXAMPLE 1 (Law of Constant Composition)

a) In a reaction, 0.455g of magnesium reacted with 2.315g of oxygen

and 0.755g of magnesium oxide was obtained. Determine the mass of
magnesium contained in a 0.500g sample of magnesium oxide?

Mg(s) + O2 (g)  MgO2(s)

0.455 g magnesium
Mass of Magnesium = 0.500 g x Mass of Magnesium = 0.301 g
0.755 g magnesium oxide

b) What masses of magnesium and oxygen must be combined to make

exactly 2.000 g of magnesium oxide?

0.455 g/0.755 g =60.3% magnesium by mass

2.000 g MgO x 60.3/100 = 1.206 g magnesium

2.000 g total mass of compound - 1.206 g magnesium = 0.794 g oxygen
Evolution of Atomic Theory
Positive charges
Dalton (1803) (indivisible particles: atoms) spread over the
entire sphere
Plum
Thomson (1904) (+ & - charges ) Pudding Model

Rutherford (1911) (protons at the nucleus & the

electrons orbiting the nucleus)

Bohr (1913) (energy levels: n)

Schrödinger (1926)
(electron-cloud model)
Subatomic Particles
• Protons (+1) and electrons (–1) have a charge; neutrons
are neutral.
• Protons and neutrons have essentially the same mass.
The mass of an electron is so small we ignore it.
• Protons and neutrons are found in the nucleus; electrons
travel around the nucleus.
Symbols of Elements

Elements are represented by a one or two letter symbol.

This is the symbol for carbon.

All atoms of the same element have the same number of

protons, which is called the atomic number, Z.

It is written as a subscript BEFORE the symbol.

The mass number is the total number of protons and

neutrons in the nucleus of an atom.

It is written as a superscript BEFORE the symbol.

Isotopes & Ions
• Isotopes are atoms that have same atomic number but
different mass numbers (or different numbers of neutrons).

• Ions are atoms that have the same atomic and mass number but
different number of electrons
+ charged ions: cations, - charged ions: anions

𝐴 ±
𝑍𝑋   protons  electrons
Example 2: Determining the Numbers of Protons
Neutrons and Electrons in Atoms and Ions

How many protons, neutrons, and electrons in (a) an atom of Au-197 and (b)
the double negatively charged ion of selenium-80

197 80 −2
79𝐴𝑢 34𝑆𝑒
# of neutron : 118 # of neutron : 46
# of e- : 79 # of e- : 36
 Atomic Mass
• Because in the real world we use large amounts of atoms
and molecules, we use average masses in calculations.
• An average mass is found using all isotopes of an element
weighted by their relative abundances. This is the
element’s atomic mass (weight : old).
• That is,

Atomic Mass = Ʃ [(isotope mass) × (fractional natural abundance)]

Note: the sum is for ALL isotopes of an element.

Bohr’s Atomic Model (H Atom and H-like Ions)
• Bohr suggested that only certain stable electron orbits
around the nucleus were allowed. The electron moves in a
circular orbit at a fixed distances from the nucleus.
The position of any particular electron is more or less well
defined in terms of its orbits (n numbers).
 The energies of electrons are quantized-electrons which
are permitted to have only specific values of energy.

Rutherford
Bohr
 Bohr Atomic Model
An electron may change energy;

 Absorption of energy: make a quantum jump to an allowed higher

energy.

After absorbing energy, an electron may jump

from the ground state to an excited state which is
any quantum state that has higher energy than the
ground state.

 Emission of energy: make a quantum jump to an allowed

lower energy.

Allowed energies are associated with energy levels or states.

Wave Mechanical Model
Niels Bohr: Exact atomic orbitals

Louis de Broglie (1924) proposed that electrons act as both waves and
particles. (Wave Particle Duality)

Heisenberg (1927) uncertainty principle: It is impossible to know

simultaneously both the momentum (mass times velocity) and the
position of a particle with certainty.

***Thus, it is not appropriate to imagine the electron circling the

nucleus in well-defined orbits.

Erwin Schrodinger (1933) proposes electron probability through wave

function equations.
Wave-Mechanical Model
Bohr model was found to Wave-mechanical model: electrons are
have some significant considered to exhibit both wavelike and
particle-like characteristics.
limitations in terms of both
position (electron orbits)  An electron is no longer considered to
and energy (quantized energy be a particle moving in a discrete orbital.
levels).
Position is considered to be the
probability of an electron’ s being at
Introduced a single quantum various locations around the nucleus.
number, n, to describe a one- The motion of the electron in an atom
dimensional orbit. cannot be precisely determined.
(Heisenberg uncertainty principle)

The quantum mechanical model uses

three quantum numbers, n, l, and ml,
which are associated with a given wave
function, also called an atomic orbital.
Quantum Numbers and Atomic Orbitals
The solution to Schrödinger’s equation for the hydrogen
atom yields a set of wave functions called (atomic) orbitals.

Atomic Orbital  electron’s radial probability distribution

(or density)
Each orbital has a characteristic shape and energy.

In wave mechanics, every electron in an atom is

characterized by four parameters, quantum numbers.

The size, shape and spatial orientation of an orbital are

specified by 3 of these quantum numbers (n, ℓ and mℓ).
Principal Quantum Number
(n): n = 1, 2, 3, …, ∞
• Identifies the shells
• Specifies the energy of an electron and the size of the orbital
(the most probable distance of an electron from the nucleus).

• All orbitals that have the same value of n are said to be in the
same shell (level).

• As n increases, the orbital becomes larger, and the electron

spends more time further from the nucleus.

• An increase in n also means that the electron has a higher

energy and is therefore less tightly bound to the nucleus.

• The total number of orbitals for a given n value is n2.

Principal Quantum Number
(n): n = 1, 2, 3, …, ∞
• For a hydrogen atom with n=1, the electron is in its ground
state; if the electron is in the n=2 orbital, it is in an excited
state.
• The energies of orbitals for a hydrogen atom, in joules, is

• Orbital energies for a hydrogen atom depend only on the

principal quantum number n.
Angular Momentum Quantum Number(ℓ):
ℓ = 0, ..., n-1.
• Specifies the shape of an orbital with a particular principal
quantum number.
• The secondary quantum number “ℓ” divides the shells into
smaller groups of orbitals called subshells (sublevels).
(from ℓ=0 to ℓ=(n-1))

ℓ=0, spherical: ℓ =1, polar: ℓ =2, cloverleaf:

(s orbital) (p orbital) (d orbital)
shells (n) and subshells (ℓ)
Principle Subshell Number of e- Total e- per
Quantum (l) per subshell shell
Number (n)
1 s 2 2
2 s 2
p 6 8

3 s 2
p 6 18

d 10
4 s 2
p 6
32
d 10
f 14

e.g. The subshell with n=2 and ℓ=1 is the 2p sub-shell;

if n=3 and ℓ =0, it is the 3s subshell, and so on.
Angular Momentum Quantum Number (ℓ):
ℓ = 0, ..., n-1.
• The value of ℓ also has a slight effect on the energy of the
subshell; the energy of the sub-shell increases with ℓ (s
< p < d < f).

For H atom; all the subshells within a

principal electronic shell have the
same energy, as do all the orbitals
within a subshell.
Magnetic Quantum Number (mℓ):
mℓ = -ℓ, ..., 0, ..., +ℓ.
• Describes the orientation in space of a particular orbital.

• Determines the number of energy states for each subshell.

• The magnetic quantum number, mℓ, only affects the

electron's energy if it is in a magnetic field.

• Given a particular ℓ, mℓ is entitled to be any integer from

-ℓ up to +ℓ.

mℓ=2ℓ +1 (TOTAL NUMBER OF ORBITALS in a subshell)

• Thus, the s subshell has only one orbital, the p subshell has
three orbitals, and so on.
Magnetic Quantum Number (mℓ):
mℓ = -ℓ, ..., 0, ..., +ℓ.

Orbital Values Number of

values for mℓ
s ℓ=0; mℓ=0 1 1 s orbital in a s
subshell
p ℓ=1; mℓ=+1, 0, -1 3 3 p orbitals in a p
subshell
d ℓ=2; mℓ=+2, +1, 0, -1, -2 5 5 d orbitals in a d
subshell
f ℓ=3; mℓ=+3, +2, +1, 0, -1, -2, -3 7 7 f orbitals in a f
subshell
Three Quantum Numbers (n, ℓ, mℓ):

Chemistry The Central Science, 13th Ed. Pearson

Chemistry The Central Science, 13th Ed. Pearson
Spin Quantum Number (ms):
ms = +½ or -½.
• Specifies the orientation of the spin axis of an electron. An
electron can spin in only one of two directions (sometimes
called up and down).
Pauli Exclusion Principle
(Wolfgang Pauli, Nobel Prize 1945)
• The Pauli exclusion principle states that no two
electrons in the same atom can have identical values
for all four of their quantum numbers.

What this means is that no more than two electrons

can occupy the same orbital, and that two electrons
in the same orbital must have opposite spins.
1

• ms= 2
1

ms= 2
Example 3
Example 4
 Example 5
What is the maximum number of electrons in an atom that can have the following
quantum numbers? Specify the orbitals in which the electron would be found.
(a) n=2; l=0; ms=-1/2
(b) n=3; l=2
Solutions to the wave-function: Atomic
Orbitals
Shells and subshells of a hydrogen atom

Energy levels are equal for

a hydrogenic atom!!

 ml  -l ,....  l 
 Solutions to the wave-function: Atomic
Orbitals
n=1 n=2 n=3
s orbitals
spherical (l=0)

p orbitals
polar (l=1)

mℓ =-1 mℓ =1 mℓ =0
Solutions to the wave-function:
Atomic Orbitals
d orbitals
(l=2)

ml=-2 ml=-1 ml=1 ml=2 ml=0

 Many electron atoms: Effective nuclear
charge
For many electron atoms, the positive
charge felt by the atom’s outer electrons
is less than the full nuclear charge
because the negative charge of the
electrons in inner shells neutralizes the
positive charge of the nucleus.

Inner electrons partially shield the outer

electrons from the nucleus

Outer electrons are attracted by only a

fraction of the full nuclear charge

* Core electrons are the electrons beneath the valence shell

Many electron atoms: Effective nuclear
charge
• Many properties depend on
attractions between
valence electrons and the
nucleus.
• Electrons are both
attracted to the nucleus
and repelled by other
electrons.
• The forces an electron
experiences depend on
both factors.
Many electron atoms: Effective nuclear
charge

Petrucci, General Chemistry 10th Ed

 Aufbau (Building-up) Principle
• Electrons fill orbitals from lowest to highest energy level.
• The order of occupation of orbitals:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p ...
Aufbau (Building-up) Principle
Pauli Exclusion Principle: Each atomic orbital
holds at most two electrons, and they spin in
opposite directions.

+1e

+1e
 Aufbau (Building-up) Principle
Hund’s rule: To minimize repulsion and maintain low energy,
electrons fill orbitals singly. When all orbitals are occupied by
at least one e-, then electrons will pair up.


Aufbau (Building-up) Principle
Hund’s rule:In its ground state, an atom adopts a
configuration with the greatest number of unpaired
electrons


Example 6
Indicate the total number of
(a) p electrons in N (Z=7)
(b)s electrons in Si (Z=14)
(c) 3d electrons in S (Z=16)
Electronic configurations:
• Electron configuration is used to
determine location of e-.
2.
• Identifies number of electrons in
ground state in each subshell at each
energy level for that atom.
Examples
Electronic configurations:

Shorthand notation for

electron configuration

•Core electrons (inner electrons) vs valence

electrons (outermost electrons)
•Closed-shell atom
Electron Configurations of Ions
• Cations: The electrons are lost from the highest energy
level (n value).
3Li+ is 1s2 (losing a 2s electron).
26Fe2+ is 1s22s22p63s23p6 3d6 (losing two 4s electrons).

• Anions: The electron configurations are filled to ns2np6;

e.g.,
• 9F– is 1s22s22p6 (gaining one electron in 2p).