ATOMIC THEORY

Theory contributions

Dalton’s atomic theory

- Applied theory of unobserved atoms (hypothetical) to observed chemical

phenomena (quantitative tangible reality)

Thomson’s atomic theory

- Plum pudding model

- Discovered electrons and measured mass/electron charge

Rutherford’s atomic theory

- Discovered that an atom consists of a nucleus surrounded by electrons

- There is a central positively charged nucleus surrounded by negatively charged
electrons
- Most of the atom’s mass is in the nucleus
- Most of the rest of the atom is empty space
Experiment:
 Beam of alpha particles aimed at a sheet of golf foil
 Screen coated with zinc sulphide surrounded the foil and flashed when hit by
an alpha particle
 Flashes determined if the foil deflected the alpha particles

Bohr’s atomic theory

- Each atom has a unique light spectra due to the spectrum produced being discrete,
not continuous

Characteristics of 3 major sub-atomic particles

- Mass: Proton and neutron has equal mass.

Electrons are very light weight.

- Charge: Electron has a (-)

Proton has a (+)
Neutron has a (0)

Wave particle duality

Light can act as a wave and a particle.

- λ: wavelength = distance
wave travels in 1 cycle (m)
- ν: frequency = number of
cycles per second (s-1 or Hz)
Radiation: λxν=c
c: velocity of light = 3 x 108 m s-1
Example: what is the frequency of light with a wavelength of 6.6x10 -7m?

 λxν=c
 (6.6x10-7m) x ν = 3 x 108 m s-1
 ν = 3 x 108 m s-1 ÷ 6.6x10-7m
 ν = 4.54x1014 Hz

Wave nature of electrons:

𝒉
- For particles: λ = 𝒎𝒗
- m: mass (kg)
- v : velocity (ms-1)
Example: Calculate the wavelength in nm of an electron weighing 9.1x10-31 kg
with a velocity of 5x106 m s-1.

 λ = h ÷ (mxv)
 Using h as Planck’s constant 6.626x10-34 J s:
 λ = 6.626x10-34 J s ÷ (9.1x10-31 kg x 5x106 m s-1)
 λ = 1.45x10-10 m
 λ = 1.45x10-10 ÷ 10-9 = 0.145 nm

Quantization of Energy: E=hxν

- E: energy (J)
- h: Planck’s constant = 6.626x10-34 J s
- ν: frequency (s-1)
- One mole of photons: (6.022 x 1023 mol¯1)’

Example: calculate the energy of photon at wavelength of 660nm.

 E=hxν
 E = 6.626x10-34 J s x ν

Convert nm to m
 λ = 660nm = 660 x 10-9m
Determine the frequency: λ x ν = c
 660 x 10-9m x ν = 3 x 108 m s-1
 ν = 3 x 108 m s-1 ÷ 660 x 10-9m
  ν = 4.54x1014 s-1
Determine the energy
 E = 6.626x10-34 J s x 4.54x1014 s-1
 E = 3x10-19J This is for one photon

Determine the energy for one mole of photons

 3x10-19J x (6.022 x 1023 mol¯1)
 180660 J/mol = 180.66 kJ/mol

Direct calculation, you could use this equation: E = hc / λ

Just make sure that the units for c and λ are the same

Neil’s Bohr Theory

- Building a simple model of an atom to understand sharp line spectra

- Electrons move in discrete orbitals around the nucleus (i.e. jumping between orbitals)
rather than a continuous spiral
o Atomic line spectra of excited atoms:
 Excited atoms emit light at certain wavelengths depending on
element
 Long wavelength = small frequency
 Any orbit and energy is possible for electrons but movement of the
charged particle should emit energy

- Electrons are restricted to QUANTIZED energy states

1
Energy of states: -C x 𝑛2
C = h x R x c = 2.1846x10-18

Therefore –C = -2.1846x10-18

h: Planck’s constant = 6.626x10-34 J s

R: Rydberg constant = 1.09974x107 m-1

c: velocity of light = 3 x 108 m s-1

n = quantum number = 1,2,3,4…

Example: Calculate the energy required to carry the H atom from ground
State (n=1) to its first excited state (n=2)
1
Energy of states = -C x 𝑛2

Calculate the energy of the n=1 and n=2 states of the H atom in
 Joules per atom and kilojoules per mole.

Calculate the energy for the ground state n=1

1
 When n = 1: -2.1846x10-18 x 12 = -2.18x10-18 J atom-1
Calculate the energy for one mole of it
 -2.18x10-18 x (6.022 x 1023 mol¯1) = -1312796 J mol-1
= -1312 kJ mol-1

Calculate the energy for excited state n=2

1
 When n = 2: -2.1846x10-18 x 22 = -5.4615x10-19 J atom-1
Calculate the energy for one mole of it
 -2.18x10-18 x (6.022 x 1023 mol¯1) = -328924 J mol-1
= -328 kJ mol-1

ΔE = Efinal – Einitial
Calculate the change in energy state
 = -1312 kJ mol-1- -328 kJ mol-1
 = -984 kJ mol-1

- Bohr’s model only works for H atom and one electron ions (e.g. He+)

L. de Broglie Theory

- All moving objects (i.e. electron, light) have particle or wave qualities
- You can calculate each object as a wavelength

Schrodinger’s wave equation

- Wave function ψ: standing wave of an electron with a particular allowed energy

- Square of wave function ψ2: probability of finding electron in the space of nucleus
- Atomic orbital: area around the nucleus where there is a high probability of finding
electron of a given energy

- Four conditions for four quantum numbers:

1
o n : (principle) orbital size and energy (-C x 𝑛2 )
o l : (angular) orbital shape/type (subshell)
o ml : (magnetic) orbital orientation. # of orbitals in subshell is 2 l + 1
o ms : electron spin (only for electrons. Not for orbitals > this has 3 QN)

- s orbital = spherical because l = 0 1 orbital (ml) 2 electrons

- p orbital = dumbbell because l =1 3 orbitals (ml) 6 electrons
- d orbital = cloverleaf because l = 2 5 orbitals (ml) 10 electrons
- f orbital = multilobe because l = 3 7 orbitals (ml) 14 electrons
 - Higher energies have electrons farther away from the nucleus
- Electrons in atoms are arranged in the order:
 Shells (n)
 Subshells (l)
 Orbitals (ml)

NOTE: Know how to draw size difference (energy level) and shape

- Subshells (e.g. s,p,d) in different shape orbitals (e.g px py pz) in a given shell (energy
level) have the SAME energy
- Principle quantum number determines energy level (e.g. p is higher than s)
- 4s orbitals are lower energy than 3d due to electron penetration phenomena

Example:

Possibilities of where electron is:

- 2, 1, 1, -½
- 2, 1, 1, ½
- 2,1,0, -½
- 2,1,0, ½
- 2,1,-1, -½
- 2,1,-1, ½
Shielding

- Shielding (electron-electron repulsion) causes the effective nuclear charge

experienced by electron to be less than actual nuclear charge.
- Outermost electron won’t feel stronger attraction than inner electrons so the outer
electrons will have more energy.

Paulie Exclusion Principle

- No electron in same atoms have same set four quantum numbers

- Each orbital can only accommodate two electrons which have opposite spin

Aufbau principle

- Electrons of atom in ground state occupy orbitals of the lowest energy

Electron filling space 2 6 10 14

Example:
Hund’s rule

- Orbitals of equal energy become half-filled with electron spins parallel before pairing
electrons

- Half full is slightly lower in energy

- Example: Copper has [Ar] 4s2 3d9 will become [Ar] 4s1 3d10 (exception=d9 and d4)
- Full shells = noble gases

Chemical periodicity

- Row = period number (n) = value of the highest energy level

n2 gives the total number of orbitals in that energy level
- Column = group = share the same valence electron configuration

Chemical reactivity

- Number of valence (outer) electrons determine chemical properties of the element

- Chemical reactions due to loss, gain or rearrangement of valence electrons
- Noble gases remain chemically stable (left side of PT will lose, right side will gain to
become noble gases) because valence shells are will be full

Ion configuration

- To form cations: remove 1 electron from subshell of highest n or n + l

- To form cations for transition metals: remove ns (e.g. 4s) electrons and then (n- l) d
electrons (e.g. 3d)
- Thus, fill 4s shell first and remove 4s shell first.

Atomic properties and periodic trends

1. Atomic size- increases down and decreases across the periodic table

- Down: outer electrons become further away from the nucleus (increase size)
- Left: effective nuclear charge pulls electrons in same shell closer (decrease size)
- Cations – smaller than the atoms they come from
o Loss of an electron causes electron/proton attraction to go up (more
pull) so there is a decrease in size.
o Fewer electrons means less shielding so stronger attraction to nucleus
- Anions – larger than the atoms they come from
o Gain of an electron causes electron/proton attraction to go down
(more repulsion) so size increases
 o More electrons mean more shielding so weaker attraction to nucleus

2. Ionization energy - energy required to remove ONE electron from a GASEOUS atom
- Decreases down a group and increases across a period. Inverse of atomic size
o First I.E: remove 1 electron only from neutral atom
(e.g. Na  Na+ + e-)
- Decreases going down and to the left as atom gets bigger and electrons in
larger (valence) orbitals are held less tightly and so are easier to remove in
the gas phase.
- It is easier to remove valence electrons than core electrons.

3. Electron affinity - energy change associated with addition of an electron to a gas-

phase atom
o Atom (g) + e-  ion- (g)
- Elements with high first I.E has higher affinity for electrons (difficult to
remove electrons but easier to acquire)
- Electron affinity is EXOTHERMIC
- Affinity for electrons increase across a period (EA becomes more negative)
and decreases down a group (EA becomes more positive)

- Note: When EA becomes more positive this means it will be ENDOTHERMIC

(wanting to lose electrons)