Professional Documents
Culture Documents
Atoms Molecules The Chemical Bond and Gas Laws Handout 2009 PDF
Atoms Molecules The Chemical Bond and Gas Laws Handout 2009 PDF
Course Overview
During the first part of the course we will be doing some introductory
‘physical’ chemistry, revision for some of you, new to others:
Atomic structure (2.1, 2.2, 2.3) and atomic mass (3.1, 3.2, 3.3);
quantum numbers and atomic orbitals (7.6, 7.7).
Electron configuration and the periodic table (7.8, 7.9)
Ionic (9.2) and covalent bonding (9.4, 9.5); Lewis dot structures (9.6,
9.7, 9.8).
Redox reactions (4.4). Oxidation numbers (4.4). Balancing redox
equations (19.1).
During the second part of the course we will introduce physical chemistry
and the gas laws (5.1-5.6):
Observations, laws, theories, models and predictions.
Gas Laws; ideal gas equation; Dalton's law of partial pressures
Recommended Reading:
‘Chemistry’; R. Chang, McGraw-Hill, 9th Ed., 2007, sections as listed.
2
1
Introduction
Atoms, Molecules and the Chemical Bond
Atoms: These are the smallest particle of an element that retain the
chemical properties of the element: átomos (Greek) = ‘uncuttable’.
Atoms are extremely small and most measure between 30-150 pm (30-150
x 10-12 m in diameter) and weigh between 1.67 × 10−27 and 4.52 × 10−25 kg.
Scale:
16 X + 8Y 8 X 2Y
Figs. 2.1 & 2.2, Chang 4
2
The Structure of the Atom:
C: Electric field on
3
The Neutron – Discovered by James Chadwick (1932).
Rutherford’s model of the atom did not account for the
following anomaly:
Nucleus:
7
4
The following symbolism is used to denote an elements make-up:
A 12
ZX 6C
= 9
Cu = 63.55g Fe = 55.85g 10
5
Do You Understand Molar Mass?
12
6
l : Angular momentum quantum number, tells us the ‘shape’ of the orbital.
The values of l depend on the principal quantum number, n.
l = 0, the electron is in an
l = 1, ….…
l = 2, ….…
l = 3, ….…
if l = 1 (p orbital), ml =
if l = 2 (d orbital), ml = 13
ms : Electron spin quantum number, tells us the orientation of the spin of the
electron. The values of ms =
Fig. 7.16
Chang
14
7
Shell – electrons with the same value of
Shapes, Size and Direction of Atomic Orbitals (Chang, 7.6 and 7.7):
An electron is more likely to be in some regions of space than others.
Strictly speaking, an orbital does not have a well defined shape as the
wave function character of the electron in an orbital stretches to infinity.
15
s Orbitals –
The larger the value of n, then the larger the orbital extends into space.
s orbitals are spherical.
16
8
p Orbitals –
The ‘dumb-bell’ shape and orientation are the same in 3p, 4p, 5p… orbitals,
although these have larger size.
17
d Orbitals –
The shape and orientation are the same in 4d, 5d,… orbitals, although
these have larger size.
Orbitals with higher energies than d-orbitals are labelled f, g, and so on are
more complicated… we are not concerned with them here.
18
9
How many electrons can an orbital hold?
19
20
10
The Order of Orbital Energies (Chang, Chapter 7.7):
Every electron in an orbital has a definite energy (quantization). The
order of orbital energies changes with the number of electrons.
n=
n=
n=
Thus, the lower n is, the lower the energy, but only orbitals in the same sub-
shell are degenerate:
n = 3; l = 1
n = 3; l = 0
n = 2; l = 1
n = 2; l = 0
11
Why does the orbital energy change from the 1 electron
atom to the many electron atoms?
23
Electrons are added one by one to the atomic orbitals, starting with the lowest
energy orbitals. e.g. N (1s) (2s) (2px) (2py) (2pz).
Because each atomic orbital can only have a maximum of 2 electrons, we can
represent the electronic configuration as:
24
12
3) Hund’s Rule:
Be 1s2 2s2
Note:
4s 3d
Cr [Ar] 4s1 3d5
13
Valence electrons: When atoms combine to form molecules, generally
only the outer or valence electrons are affected.
You will need to know the valence electrons of all the elements from the
first 2 rows of the periodic table. 27
Fluorine has a high electron affinity and likes to gain and electron:
e- + F F -
28
14
Variation of the First Ionization Energy with Atomic Number
Filled n = 1 shell
Fig. 8.11, Chang
Filled n = 2 shell
Filled n = 3 shell
Filled n = 4 shell
Filled n = 5 shell
29
30
15
Nature of Ionic Solids:
NaCl: Extended lattice containing ions rather than distinct molecular entities
Strong electrostatic binding forces. High melting point.
Lewis structure of F2
F F
F F
Lone pairs:
32
16
Guidelines for Sharing Electrons:
H – must attain the electronic configuration of He i.e. two electrons.
Other atoms: like to form bonds until they are surrounded by 8 valence
electrons (octet rule), works particularly well for elements in 2nd period.
H + O + H H O H or H O H
O C O or
8e- 8e- 8e-
N N or
8e-8e-
33
General Approach:
2)
3) Link atoms with single bonds. Add lone pairs to complete an octet for all
atoms except hydrogen.
4)
34
17
Write the Lewis structure of nitrogen trifluoride (NF3)
Step 1:
Step 2:
F N F
F
35
Step 2:
2 single bonds ( )= 2–
O C O 1 double bond =
8 lone pairs ( )=
Total =
O
36
18
Two possible skeletal structures of formaldehyde (CH2O)
H
H C O H C O
H
The sum of the formal charges of the atoms in a molecule or ion must
equal the charge on the molecule or ion.
37
C– e- 2 single bonds ( )=
H C O H O– e- 1 double bond =
2H – e- 2 lone pairs ( )=
e- Total =
formal charge
=
on C
formal charge
=
on O
H C – e- 2 single bonds ( )=
C O O – e- 1 double bond =
H 2H – e- 2 lone pairs ( )=
e- Total =
formal charge
=
on C
formal charge
=
on O 38
19
Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there are no formal
charges is preferable to one in which formal charges are present.
2. Lewis structures
39
O2 + 4e- 2O2-
Overall:
‘OILRIG’ : 40
20
These reaction are called reduction-oxidation reactions or REDOX reactions.
The processes of reduction and oxidation always occur together.
42
21
Is it a Redox Reaction?
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
43
44
22
Balance the Reduction Half Reaction:
8H+(aq) + MnO4- (aq) + 5e- → Mn2+(aq) + 4H2O (l)
K:
O: Add
H: Add
E: Add
S: Specify the states of the reaction components.
23
Redox Titrations
A titrant (of known concentration) is added, using a
burette, to a known volume of an analyte (of unknown
concentration).
3. From the stoichiometry of the balanced equations and the amount of the
titrant added at the equivalence point, determine the amount of analyte.
47
48
24
An Introduction to the Gas Laws
Chang, Chapter 5
Physical Characteristics of Gases:
Gases assume the volume and shape of their containers.
Gases are the most compressible state of matter.
Gases will mix evenly and completely when confined to the same container.
Gases have much lower densities than liquids and solids.
49
Units of Pressure
1 Pascal (Pa) = 1 N m-2
(1 N = 1 J m-1; 1 Pa = 1 J m-3)
1 atm = 760 mmHg = 760 torr Fig 5.3, Chang Hg liquid
25
Experimental Variable: Temperature
Celsius temperature (θ) is referenced to the freezing point of water and is
measured in degrees Celsius (°C).
51
52
26
Boyle’s Law: The Pressure-Volume Relationship
Boyle studied the pressure-volume relationship of a fixed
amount of gas at a constant temperature:
Robert Boyle
(1627-1691)
Irish Chemist
Boyle’s Law:
54
27
Gay-Lussac’s or Charles’s Law: The
Temperature-Volume Relationship
Gay-Lussac rationalised Charles’s earlier
observations on the effects of heating a fixed
amount of gas at constant pressure: Joseph Gay-Lussac Jacques Charles
(1778-1850) (1746-1823)
Fig 5.8,
Chang
Charles’s Law:
56
28
Avogadro’s Law: The Volume-Amount Relationship
‘At constant pressure and temperature, the volume of a gas is
directly proportional to the number of moles of the gas present’
57
An Ideal Gas
Molecules in an ideal gas do not attract or repel each other.
The total volume of the molecules is negligible in comparison with the
volume of the container.
Real gases rarely deviate significantly from ideal behaviour.
58
29
Argon is an inert gas used in lightbulbs to retard the vaporization of the
filament. A certain lightbulb containing argon at 1.20 atm and 18 °C is
heated to 85 °C at constant volume. What is the final pressure of
argon in the lightbulb (in atm)?
59
Calc. the density of H2O(vap) at 100 °C and 1 atm pressure. The density
of H2O(liq.) at 0 °C is 1 g/cm3, compare. [M(H2O) = 18.02 g/mol]
60
30
Dalton’s Law of Partial Pressures:
Dalton's law says that the total pressure is the sum of the partial pressures:
It can be assumed that the gas is saturated with water. The value of PH2O
is equal to the saturated vapour pressure of water at that temperature.
31
O2 gas generated by the decomposition of KClO3(s) is collected over
water (Fig, 5.15). The volume of O2 collected at 24 °C and a pressure
of 762 mmHg is 128 mL. Calculate the mass (in grams) of O2 gas
obtained. The pressure of water vapor at 24 °C is 22.4 mmHg.
63
64
32
Appendix: Illustration of the Gas Laws, Chang Figure 5.6
Boyle’s Law
P P P
Boyle’s Law
65
Charles’s Law
Heating or cooling a gas at constant pressure
P P P
Charles’s Law
V = (nR) T nR is constant
P P
66
33
Charles’s Law
Heating or cooling a gas at constant volume
P P P
Charles’s Law
P = (nR) T nR is constant
V V
67
Avogadro’s Law
P P P
Gas cylinder
Add gas
Remove gas molecules
(Volume (Volume
decreases) increases)
Valve
Avogadro’s Law
(RT) RT
V= n is constant
P P
68
34