Chemistry

Unit 3: Atomic Structure

 Basics of the Atom

Subatomic Location in
Particle
Charge Mass
the Atom
proton 1+ in nucleus ~ 1 a.m.u.

neutron 0 in nucleus ~ 1 a.m.u.

electron 1– around nucleus ~ 0 a.m.u.

a.m.u.: unit used to measure mass of atoms

“atomic mass unit”
atomic number: # of p+ 10
-- the whole number
on Periodic Table Ne
-- determines identity 20.1797
of the atom

mass number: (# of p+) + (# of n0)

(It is NOT on “the Table.”)

To find net charge on an atom, consider

e–
p+ and ____.
____
 ion: a charged atom

anion: a (–) ion cation: a (+) ion

-- more e– than p+ -- more p+ than e–
-- formed when -- formed when
atoms gain e– atoms lose e–

I think that anions are negative ions.

“When I see a cation, I see a positive ion;

that is, I… C A + ion.”

 Other Mnemonic Devices

Metals form positive

ions

Cations are “paws”itive

 Net Atomic Mass Ion
Description
Charge Number Number Symbol

15 p+
16 n0 3– 15 31 P3–
18 e–
38 p+
50 n0 2+ 38 88 Sr2+
36 e–
52 p+
76 n0 2– 52 128 Te2–
54 e–
19 p+
20 n0 1+ 19 39 K+
18 e–
Isotopes: different varieties of an element’s atoms
-- have diff. #’s of n0; thus, diff. mass #’s
-- some are radioactive; others aren’t
All atoms of an element react the same chemically.

Isotope Mass p+ n0 Common Name

H–1 1 1 0 protium
H–2 2 1 1 deuterium
H–3 3 1 2 tritium
C–12 atoms C–14 atoms
6 p+ 6 n 0 6 p+ 8 n 0
stable radioactive
 Complete Atomic Designation
…gives very precise info about an atomic particle

mass # charge (if any)

element
symbol
atomic #

125 –
53
I
Goiter due to iodine is now
lack of iodine added to salt
 Complete
Protons Neutrons Electrons Atomic
Designation
238
92 146 92 U
92
23 +
11 12 10 Na
11
79 2–
34 45 36 Se
34
59 3+
27 32 24 Co
27
37 –
17 20 18 Cl
17
55 7+
25 30 18 Mn
25
Radioactive Isotopes: have too many or too few n0
Nucleus attempts to attain a lower
energy state by releasing extra
radiation
energy as __________.
e.g., a- or b-particles, g rays

half-life: the time needed for

½ of a radioactive
sample to decay
into stable matter
e.g., C–14: half-life is 5,730 years
decays into stable N–14
 Say that a 120 g
= C–14
sample of C-14 is
= N–14
found today…

Years g of C–14 g of N–14

from now present present
0 120 0
5,730 60 60
11,460 30 90
17,190 15 105
22,920 7.5 112.5
Half Life Graph (Sr-90 Activity)
 Average Atomic Mass (AAM)
This is the weighted average mass of all atoms of
an element, measured in a.m.u.
Ti has five naturally-
occurring isotopes
For an element with
isotopes A, B, etc.:
AAM = Mass A (% A) + Mass B (% B) + …

% abundance
(use the decimal form of the %
e.g., use 0.253 for 25.3%)
 Lithium has two isotopes.
Li-6 atoms have mass 6.015 amu;
Li-7 atoms have mass 7.016 amu.
Li-6 makes up 7.5% of all Li atoms.
Find AAM of Li. Li batteries
AAM = Mass A (% A) + Mass B (% B)
AAM = 6.015 amu (0.075) + 7.016 amu (0.925)

AAM = 0.451 amu + 6.490 amu

AAM = 6.94 amu
** Decimal number on Table refers to…
molar mass (in g) OR AAM (in amu).
6.02 x 1023 atoms 1 “average” atom
 %
Isotope Mass
abundance
Si-28 27.98 amu 92.23%
Si-29 28.98 amu 4.67%
Si-30 ? 3.10%
AAM = MA (% A) + MB (% B) + MC (% C)
28.086 = 27.98 (0.9223) + 28.98 (0.0467) + X (0.031)
28.086 = 25.806 + 1.353 + 0.031X
28.086 = 27.159 + 0.031X
0.927 = 0.031X
0.031 0.031
X = MSi-30 = 29.90 amu
Historical Development of the Atomic Model

Greeks (~400 B.C.E.)

Democritus & Leucippus

Matter is discontinuous (i.e., “grainy”).
“atomos” = uncuttable or indivisible

Greek model
of atom

Solid and INDESTRUCTABLE

 Hints at the Scientific Atom

** Antoine Lavoisier:
law of conservation of mass
mass R = mass P

** Joseph Proust (1799):

law of definite proportions: every
compound has a fixed proportion

e.g., water…………………….. 8 g O : 1 g H
chromium (II) oxide……. 13 g Cr : 4 g O
 Hints at the Scientific Atom (cont.)
** John Dalton (1803):
law of multiple proportions:
When two different compounds
have same two elements, equal
mass of one element results in
integer multiple of mass of other

2
e.g., water…………………….. 8 g O : 1 g H
hydrogen peroxide..…….16 g O : 1 g H

3
chromium (II) oxide……. 13 g Cr : 4 g O
chromium (VI) oxide……13 g Cr : 12 g O
John Dalton’s Atomic Theory (1808)

1. Elements are made of

indivisible particles called atoms.

2. Atoms of the same element are exactly

alike; in particular, they have the same mass.
3. Compounds are formed by
Dalton’s
the joining of atoms of two
model
or more elements in fixed,
of atom
whole number ratios.
e.g., 1:1, 2:1, 1:3, 2:3, 1:2:1

NaCl, H2O, NH3, Fe2O3, C6H12O6

** William Crookes
(1870s):
Rays causing
shadow were
emitted from
cathode.

Maltese cross CRT

radar screen computer

television
monitor
J.J Thomson (~1900)
J.J. Thomson discovered
that “cathode rays” are…
…deflected by electric
and magnetic fields
electric field lines J.J. Thomson
“cathode rays” ++++++

Crooke’s tube – – – – – –
phosphorescent
… (–) particles electrons screen
William Thomson (a.k.a., Lord Kelvin):
Since atom was known to be
electrically neutral, he proposed
the plum pudding model.

-- Equal quantities of (+) and (–) Lord Kelvin

charge distributed uniformly
++ ++
–
in atom. –
–
–
-- (+) is ~2000X more massive + ++ +
–
–

–
– –
than (–) + ++ –
–

plum
pudding Thomson’s plum
pudding model
Ernest Rutherford (1909)
Gold Leaf Experiment

Beam of a-particles (+) directed

at gold leaf surrounded by
phosphorescent (ZnS) screen. gold
leaf
particle
a-source beam

lead ZnS
block screen
 Most a-particles passed through, some angled
slightly, and a tiny fraction bounced back.

Conclusions:
1. Atoms are mostly empty space
2. (+) particles are concentrated at center
nucleus = “little nut”
3. (–) particles orbit nucleus
 Rutherford’s
Dalton’s
Thomson’s(also ModelModel
thePudding
Plum Greek) Model

–
–
– +
+
–
+
– +
–
+ N+ –
+–
–
– –
+ – –

+– + + –
– –
** James Chadwick
discovered neutrons in 1932
n0 have no charge
and are hard to detect
purpose of n0 = stability of nucleus
Chadwick

And now we know of many

other subatomic particles:
quarks,
muons,
positrons,
photo from liquid neutrinos,
H2 bubble chamber pions, etc.
 Discovery of the Neutron

9 4 12 1
4 Be +
2 He 6 C +
0 n

James Chadwick bombarded beryllium-9 with alpha particles,

carbon-12 atoms were formed, and neutrons were emitted.

Dorin, Demmin, Gabel, Chemistry The Study of Matter 3rd Edition, page 764 *Walter Boethe
 Recent Atomic Models
Max Planck (1900): Proposed that
amounts of energy are quantized
 only certain values are allowed
Niels Bohr (1913): e– can possess
only certain amounts of energy, and
can therefore be only certain
distances from nucleus.

planetary
N
(Bohr) e– found e– never
model here found here
 Bohr Atom
The Planetary Model of the Atom
 Bohr’s Model

Nucleus

Electron

Orbit

Energy Levels
 quantum mechanical model
electron cloud model
charge cloud model

Schroedinger, Pauli, Heisenberg, Dirac (up to 1940):

According to the QMM, we never know for certain
where the e– are in an atom, but the equations of the
QMM tell us the probability that we will find an
electron within a certain distance from the nucleus.
 Electron Cloud Model
• Orbital (“electron cloud”) instead of “orbits”
– Region in space where there is 90% probability
of finding an electron
90% probability of Electron Probability vs. Distance
40
finding the electron

Electron Probability (%)

30

20

10

0
0 50 100 150 200 250
Distance from the Nucleus (pm)

Orbital
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
 Models of the Atom Review
"In science, a wrong theory can be valuable and better than no theory at all."
- Sir William L. Bragg
e
e + +
e -
e
+ + -
+e e
+ e - +

- -
e
+ e + e

Dalton’s model
Greek model Thomson’s plum-pudding Rutherford’s model
(400
(1803)
B.C.) model (1897) (1909)

Bohr’s model Charge-cloud model

(1913) (present)

Dorin, Demmin, Gabel, Chemistry The Study of Matter , 3rd Edition, 1990, page 125
 Models of the Atom Timeline
e
e + e + -
+
e
+ -
+e e
+e - +

- -
e
+ e + e

Dalton’s model
Greek model Thomson’s plum-pudding Rutherford’s model Bohr’s model Charge-cloud model
(1803)
(400 B.C.) model (1897) (1909) (1913) (present)

1803 John Dalton 1897 J.J. Thomson, a British
scientist, discovers the electron,
pictures atoms as
tiny, indestructible leading to his "plum-pudding"
model. He pictures electrons
particles, with no
internal structure. embedded in a sphere of
positive electric charge.
1911 New Zealander
Ernest Rutherford states
that an atom has a dense,
positively charged nucleus.
Electrons move randomly in
the space around the nucleus.
1913 In Niels Bohr's
model, the electrons move
in spherical orbits at fixed
distances from the nucleus.
1926 Erwin Schrödinger
develops mathematical
equations to describe the
motion of electrons in
atoms. His work leads to
the electron cloud model.

1800 1805 ..................... 1895 1900 1905 1910 1915 1920 1925 1930 1935 1940 1945

1924 Frenchman Louis 1932 James

1904 Hantaro Nagaoka, a de Broglie proposes that Chadwick, a British
Japanese physicist, suggests moving particles like electrons physicist, confirms the
that an atom has a central have some properties of waves. existence of neutrons,
nucleus. Electrons move in Within a few years evidence is which have no charge.
orbits like the rings around Saturn. collected to support his idea. Atomic nuclei contain
neutrons and positively
charged protons.
Dorin, Demmin, Gabel, Chemistry The Study of Matter , 3rd Edition, 1990, page 125
 Light
When all e– are in lowest possible energy state,
ground state
an atom is in the ____________.
e.g., He: 2 e-, both in 1st energy level
ENERGY
(HEAT, LIGHT,
ELEC., ETC.)

If “right” amount of energy is absorbed by an e–, it can

“jump” to a higher energy level. This is an unstable,
excited state
momentary condition called the ____________.
e.g., He: 1 e- in 1st E level, 1 e- in 2nd E level
When e– falls back to a lower-energy, more stable
orbital (it might be the orbital it started out in, but it
might not), atom releases the “right” amount of
energy as light.

EMITTED LIGHT
Any-old-value of energy to be
absorbed or released is
NOT OK. This explains
the lines of color in an
emission spectrum.
Emission Spectrum for a Hydrogen Atom

Lyman series:
e– falls to 1st energy level

Balmer series:
e– falls to 2nd energy level
H discharge
Paschen series: tube, with power
supply and
e– falls to 3rd energy level
spectroscope

typical emission spectrum

Lyman Balmer Paschen
(UV) (visible) (IR)
6TH E.L.
5TH E.L.
4TH E.L.

~
~
~
~

~
3RD E.L.

2ND E.L.

1ST E.L.
electromagnetic radiation (i.e., light)

-- waves of oscillating electric (E)

and magnetic (B) fields
-- source is… vibrating electric charges

B
 Characteristics of a Wave
crest
amplitude A

trough

wavelength l

frequency: the number of cycles per

unit time (usually sec)
-- unit is Hz, or s–1 or 1/s
electromagnetic spectrum: contains all of the “types” of
light that vary according to frequency and wavelength

microwaves
radio waves

IR

UV

gamma rays
X-rays
visible

cosmic rays
ROYGBV
750 nm 400 nm
large l small l
-- visible spectrum ranges from
low f only ~400 to 750 nm (a very high f
low energy narrow band of spectrum) high energy
Albert Michelson (1879)
-- first to get an accurate
value for speed of light

Albert Michelson
(1852–1931)

The speed of light in

a vacuum (and in air)
is constant:
c = 3.00 x 108 m/s

-- Equation: c=fl
In 1900, Max Planck assumed
that energy can be absorbed
or released only in certain
discrete amounts, which he
called quanta.

Later, Albert Einstein dubbed Max Planck

(1858–1947)
a light “particle” that carried a
quantum of energy a photon.

-- Equation: E=hf

E = energy, in J
h = Planck’s constant Albert Einstein
= 6.63 x 10–34 J∙s (i.e., J/Hz) (1879–1955)
A radio station transmits
at 95.5 MHz (FM 95.5).
Calculate the wavelength
of this light and the energy
of one of its photons.

c 3.00 x 108 m/s

c=fl  l = 6 = 3.14 m
f 95.5 x 10 Hz

E = h f = 6.63 x 10–34 J/Hz (95.5 x 106 Hz)

= 6.33 x 10–26 J
 Electron Cloud Model
• Orbital (“electron cloud”) instead of “orbits”
– Region in space where there is 90% probability
of finding an electron
90% probability of
finding the electron
Orbital Shape

Orbital

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

Shapes of s, p, and d orbitals
 p-Orbitals

px pz py

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 335

 s, p, and d-orbitals

s orbitals: p orbitals: d orbitals:

Each holds 2 Each of 3 sets holds Each of 5 sets holds
electrons 2 electrons = 6 2 electrons
(outer orbitals of electrons = 10 electrons
Groups 1 and 2) (outer orbitals of (found in elements
Groups 3 to 8) in third period
and higher)
Kelter, Carr, Scott, , Chemistry: A World of Choices 1999, page 82
f orbitals
 Relative Sizes 1s and 2s

1s 2s
Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 334
Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
 Periodic Patterns
n s block p block
1 1s 1s

2 2s 2p

3 3s d block (n-1) 3p

4 4s 3d 4p

5 5s 4d 5p

6 6s 5d 6p

7 7s 6d 7p

6 4f
f (n-2) 7 5f

block
Sections of Periodic Table to Know

s-block
p-block

d-block

f-block
 Energy Level Diagram of a Many-Electron Atom
6s 6p 5d 4f

32

5s 5p 4d

18

4s 4p 3d

18
Arbitrary
Energy Scale Each
3s 3p
orbital
8
can only
2s 2p
hold 2 e-
8

Start from
the bottom
1s
and add e-
2

NUCLEUS
O’Connor, Davis, MacNab, McClellan, CHEMISTRY Experiments and Principles 1982, page 177
You don’t have to memorize the
order…just start at the
beginning and fill in e-…
 Periodic Patterns
• Example - Hydrogen
1
2
3
4
5
6
7

1 e- in “1s”
1s 1 orbital

1st Period (row) s-block

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 Writing Electron Configurations:
Where are the e–? (probably)
H 1s1
He 1s2
Li 1s2 2s1
N 1s2 2s2 2p3
Al 1s2 2s2 2p6 3s2 3p1
Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2
As 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3
Xe 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6
Filling
Order
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6…
Shorthand Electron Configuration (S.E.C.)
To write S.E.C. for an element:
1. Put symbol of noble gas that precedes
element in brackets.
2. Continue writing e– config. from that point
S [ Ne ] 3s2 3p4
Co [ Ar ] 4s2 3d7
32
In [ Kr ] 5s2 4d10 5p1 Ge
72.61

Cl [ Ne ] 3s2 3p5
Rb [ Kr ] 5s1
 Shorthand Configuration

A neon's electron configuration (1s22s22p6)

B 3rd energy level (or 3rd period)

[Ne] 3s1
C 1 electron in the s orbital

D orbital shape (s,p,d,f…etc.)

Na = [
1s 22s22p6] 3s1 electron configuration
Shorthand Configuration Review
Element symbol Electron configuration
Ca [Ar] 4s2
V [Ar] 4s2 3d3
F [He] 2s2 2p5
Ag [Kr] 5s2 4d9
I [Kr] 5s2 4d10 5p5
Xe [Kr] 5s2 4d10 5p6 or [Xe]
Fe 22p64s
[He] 2s[Ar] 3s223d
3p664s23d6
Sg [Rn] 7s2 5f14 6d4
Three Principles about Electrons
3d10…
Aufbau Principle: 4s2
e– will fill the lowest-energy 3p6
3s2
orbital available 2p6
2s2
Hund’s Rule: 1s2
for equal-energy orbitals (p, d)
each must have one e– before
any take a second Friedrich Hund

Pauli Exclusion Principle:

two e– in same orbital
have different spins
Wolfgang Pauli
 Orbital Diagrams

…show spins of e– and orbital location

O 1s22s22p4

1s 2s 2p 3s 3p

P 1s22s22p63s23p3

1s 2s 2p 3s 3p
The Importance of Electrons

orbitals: regions of space where an e– may be found

In a generic e– config (e.g., 1s2 2s2 2p6 3s2 3p6…):

coefficient # of energy level
superscript # of e– in those orbitals
In general, as energy level # increases, e–…

HAVE MORE AND ARE FURTHER

ENERGY FROM NUCLEUS
 16
S
Electron Configuration 32.066

• Longhand Configuration

S 16e- 1s2 2s2 2p6 3s2 3p4

Kernel (Core) Valence Electrons

Electrons (Highest energy level)

• Shorthand Configuration

S 16e- 2
[Ne] 3s 3p4
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kernel (core) electrons: valence electrons:
in inner energy level(s); in outer energy level
close to nucleus
INVOLVED IN
CHEMICAL
BONDING

He: 1s2 (2 valence e–)

Ne: [ He ] 2s2 2p6 (8 valence e–)
Ar: [ Ne ] 3s2 3p6 (8 valence e–)
Kr: [ Ar ] 4s2 3d10 4p6 (8 valence e–)

Noble gas atoms have FULL valence orbitals.

They are stable, low-energy, and unreactive.
 Other atoms “want” to be like noble gas atoms…
** So, they lose or gain e–...
octet rule: the tendency for atoms to fill valence
orbitals completely with 8 e– (outer E level)
doesn’t apply to He, Li, Be, B (which require 2)
or to H (which requires either 0 or 2)…“duet rule”
fluorine atom, F chlorine atom, Cl
9 p+, 9 e– How to be like 17 p+, 17 e–
a noble gas…? [Ne] 3s23p5
[He] 2s22p5
gain 1 e– or lose 7 e-? gain 1 e– or lose 7 e-?
9 p+, 10 e– F– 17 p+, 18 e– Cl–
F is more stable as Cl is more stable as
an F– ion a Cl– ion
 lithium atom, Li sodium atom, Na
3 p+, 3 e– How to be like 11 p+, 11 e–
a noble gas…?
[He] 2s1 [Ne] 3s1
lose 1 e– or gain 7 e-? lose 1 e– or gain 7 e-?
3 p+, 2 e– Li+ 11 p+, 10 e– Na+
Li is more stable Na is more stable
as the Li+ ion. as Na+ ion
 Know charges on these columns of Table:
Group 1: 1+
Group 2: 2+
Group 3: 3+
Group 5: 3–
1+ Group 6: 2– 0
2+ Group 7: 1– 3+ 3– 2– 1–
Group 8: 0
Periodic Patterns and Charge Trends
n s p
+1 +2
1 d +3 -3 -2 -1 1s

2
Variable Charge
3
4
5
6
7
6
f (n-2) 7
 Naming Ions
Cations use element name and then say “ion”
e.g., Ca2+ calcium ion
Cs1+ cesium ion
Al3+ aluminum ion
Anions change ending of element name to “ide”
and then say “ion”
e.g., S2– sulfide ion
P3– phosphide ion
N3– nitride ion
O2– oxide ion
Cl1– chloride ion
Extra Slides