Chemistry 14: The Fundamentals of General Chemistry I

CHEMISTRY 14
The Fundamentals of General Chemistry I

Noel S. Quiming
Department of Physical Sciences and Mathematics
2nd Semester || AY 2010-2011 || Section TFC

Tuesdays and Fridays: 10:00-11:30AM GAB 105 Notes by Alvin J. Logronio
Table of Contents
Atomic Structure
The Development of the Different Atomic Models 1
The Subatomic Particles 2
Quantum Mechanical Model and Quantum Numbers 3
The Periodic Table 6
Periodicity of Properties 7
The Chemical Bond
Ionic or Electrovalent Bond 8
The Covalent Bond 9
Properties of Covalent Bonds 14
Theories on Covalent Bonds 14
Changes in Matter
Chemical Changes 16
The Mole Concept 16
Empirical and Molecular Formula 18
Stoichiometry19
Nuclear Changes 22
Nuclear vs. Chemical Change 22
Types of Radioactive Decay 23
Types of Nuclear Changes 24
Phases of Matter
Intermolecular Forces of Attraction 25
Comparison of the Phases of Matter 26
Phase Changes and Phase Diagrams 26
The Gaseous State 27
Kinetic Molecular Theory 27
The Gas Laws 28
Dalton's Law of Partial Pressures 30
Deviations from Ideal Behavior 30
The Liquid State 30
The Solid State 31
Solutions
The Dissolution Process 31
Factors Affecting Solubility 32
Types of Solutions 33
Concentration33
Concentration Units 33
Dilution 34
Colligative Properties 34
Acids and Bases
Definitions 35
Types of Acids 36
Titration and Neutralization 36
Chemical Thermodynamics
Basic Concepts 37
The First Law of Thermodynamics 38
Heats of Reaction 39
The Second Law of Thermodynamics 41
Entropy41
Gibb’s Free Energy (ΔG) 41
Third Law of Thermodynamics 43
Chemical Kinetics
Theories on Reaction Rates 44
Factors Affecting Rates of Reactions 44
Chemical Equilibrium
Molecular Equilibrium 45
Definitions 45
Factors Affecting Equilibrium 46
Ionic Equilibrium 48
ii | Chemistry 14: Fundamentals of General Chemistry I

Atomic Structure
The Development of the Different Atomic Models
Democritus
- proposed that matter is made up of small indivisible “atoms”
- small, hard, infinite and has different shapes
- found when something is divided and divided: Ends up with an atom of gold
- said that they are always moving and capable of joining
- nobody believed him
- Aristotle was more believed, where he said that the world is made up of 4 elements
John Dalton - Billiard Ball Model

Potulates:
- matter is made up of tiny indivisible atoms
- all atoms are identical
- different elements have different atoms
- compounds are made by joining atoms
- was believed for 100 years until the discovery of subatomic particles
J.J. Thompson - Plum Pudding/Raisin Bread Model

- he discovered the electron using a cathode ray tube
- seen through a neutral gas acting like its negatively charged
- this proved that the atom was divisible
- he showed that there were negatively charged “corpuscles” (electrons) in matter
- he proposed that there must be another positively charged particle to neutralize the charge
- was believed for only 5 years
Dalton’s model was similar to Thompson’s model by both believing that the atom is solid.
Ernest Rutherford - Nuclear Model

- first to propose a nucleus in the atom
- performed the gold foil experiment
- a stream of alpha rays were aimed perpendicularly at a gold foil
- most light passed through the film and some were reflected
- proved that the atom is not solid (mostly empty space)
- it must have a very small dense area of positive charge
- the positive particle proton negated the electron and is 2000 times more massive
- no results would give a complete description of the electron
- he just assumed they were scattered around the nucleus
Limitations of Rutherford
- What holds the nucleus?
- Why don’t the electrons collapse into the nucleus?
- Wrong proportion of masses with number of particles.
- suggested that there was another particle
James Chadwick
- he discovered the neutron
- showed that the nucleus contained protons and neutrons
- nucleons: protons and neutrons
Modern Model (Rutherford) vs. Dalton

- atoms are divisible
- atoms of the same element may not be identical
- atoms of an element can be changed into another element by nuclear reactions
Noel S. Quiming Notes by A-Log | 1

The Subatomic Particles
Atomic Mass Unit (amu)

- mass of 1/12 of a 12C atom
Isotopic Notation
A A
or
Z
X XZ
where: A is the mass no. and Z is the atomic no.
Atomic No. (Z) = No. of protons

= No. of electrons (if neutral)
Mass No. (A) = No. of protons + No. of neutrons

= No. of electons + No. of neutrons (if neutral)
= Z + No. of Neutrons
For Cations (+): No. of protons > No. of electrons

For Anions (-): No. of Protons < No. of electrons
Charge = algebraic sum of No. of protons and No. of electrons
No. of protons No. of electrons No. of neutrons

24
12
Mg2+ 12 10 12
32
16
S2- 16 18 16
63
30
Zn2+ 30 28 33
Isotopes
- atoms of the same element that have the same No. of protons but different No. of neutrons
- same Z but different A
Examples: 1H 2H 3H; 12C 13C 14C; 235U 238U
No. of protons No. of neutrons Mass Number

1
H (protium) 1 0 1
2
H (deuterium) 1 1 2
3
H (tritium) 1 2 3
H = proton
+
C - used in NMR (Nuclear Magnetic Resonance)

13
C - used in carbon dating t½ = 5700 years

14
Atomic Mass
- averaged from the masses of isotopes
- uses the relative abundance of isotopes
Example:
Given:
35
Cl : relative abundance = 75.77% Atomic Mass = 34.968 amu
37
Cl : relative abundance = 24.23% Atomic Mass = 36.965 amu
2 | Chemistry 14: Fundamentals of General Chemistry I

Average Atomic Mass = (relative abundance 1)(atomic mass 1) +
(relative abundance 2)(atomic mass 2)
Average Atomic Mass = (0.7577)(34.968) + (0.2423)(36.965)
= 35.45 amu
Isobars - atoms of different elements but with the same Mass No. (same A)
Isotones - atoms with the same No. of neutrons
Niels Bohr - Planetary Model

- electrons move in ciruclar orbits (orbitals)
- energies are quantized meaning they have definite values
- electrons need to absorb energy to jump across orbitals
- minimum energy needed = energy difference (E =∆E)

1 ∆E = E2 − E1
E = −Rh
n2 1 1
= −Rh 2 − −Rh
n n21
2
Rh = Rydberg constant 1 1
= −Rh 2 − 2
= 2.1 × 10−18 J n2 n1
- after jumping into the excited state, electrons need to go back to the original orbital releas-
ing light energy.
hc h = P lanck s constant c = Speed of Light

E=
λ = 6.63 × 10−34 Js = 3.0 × 108 m/s
Example:
n=5→n=1

1 1 hc (6.63 × 10−34 Js)(3.0 × 108 m/s) 1 × 104 nm
∆E = −Rh − 2 λ= =
n2f ni E 2.016 × 10−18 J 1m
= 98.66 nm
1 1
= −2.1 × 10−18 2
− 2
1 5
= −2.016 × 10−18 J
Application:
Flame Tests - wavelengths resulting from energy release result in different colors of light
Limitations of Bohr
- cannot describe a multi-electron model
Quantum Mechanical Model and Quantum Numbers

Erwin Schrödinger - Quantum Mechanical Model
- electrons move in a 3D space (electron cloud)
Orbitals
Node - a region in space where there is zero probability of finding an electron
s orbitals: s
p orbitals: px, py, pz
d orbitals: dxy, dxz, dyz, dz^2, dx^2-y^2
Quantum Numbers
- sets of numbers that are used to describe electrons

Symbol Possible Values Comments
Principal n positive integers - describes the
(1, 2, 3, ...) energy level of an
electron
Higher n: n = 1 (K shell) - describes the size
- higher energy = 2 (L shell) of the electron cloud
- bigger atom/ = 3 (M shell) - main energy level/
electron cloud and so on... shell
Angular Momentum l n=1 l=0 - describes the
or Azimuthal n=2 l = 0, 1 shape of the electron
l = 1 (s shell) n=3 l = 0, 1, 2 cloud
= 2 (p shell) n=4 l = 0, 1, 2, 3 - describes the sub-
= 3 (d shell) shell/sublevel
= 4 (f sublevel)
Magnetic m or ml l=1 m = -1, 0, +1 - determines the ori-
l=2 m = -2, -1, 0, entation of space of
+1, +2 the electron cloud
l=3 m = -3, -2, -1, - describes the
0, +1, +2, +3 orbital
Spin s or ms +½, -½ - describes the direc-
tion of the rotation of
the orbital
Pauli’s Exclusion Principle

- no two electrons can have the same set of quantum numbers
- same n: same shell
- same l: same subshell
- same m: same orbital
- electrons in the same orbital cannot have the same s
- orbitals can only accomodate two electrons
No. of orbitals No. of electrons

n=1 1 2
n=2 4 8
n=3 9 32
Electron Configuration
AUFBAU Building Principle
- lower energy levels are filled up first
n+l rule
- the higher the n+l value, the higher the energy of the subshell
- determine the energy level of subshells
Example:
4s: n+l = 4+0 = 4
3d: n+l = 3+2 = 5
4p: n+l = 4+1 = 5
- If both n+l values are equal, you describe the one with the higher shell first
Examples:
1
H: 1s1
2
He: 1s2

6
2
C: 1s 2s 2p
2 2

2p: ↓_ ↓_ __
2s: ↓↑
Ground state: 1s: ↓↑
- orbitals in the same subshell are degenerate with one another (have the same energy)
- p orbitals: ↓_ ↓_ __ = ↓_ __ ↓_ = __ ↓_ ↓_
Hund's Rule of maximum Multiplicity

- one electron is filled in each orbital first before pairing with an unpaired one
Atoms at ground state can undergo excitation into an excited state:
6
2
C: 1s 2s 2p
2 2

2p: ↓_ ↓_ __
2s: ↓↑

2p: ↓_ ↓_ ↓_
2s: ↓_
Excited state: 1s: ↓↑
Quantum Numbers for electrons in an orbital:
1s: ↓↑ (1, 0, 0, -½), (1, 0, 0, +½)

2s: ↓↑ (2, 0, 0, -½), (2, 0, 0, +½)
2p: ↓↑ ↓↑ ↓↑ (2, 1, -1, -½), (2, 1, -1, +½)
(2, 1, 0, -½), (2, 1, 0, +½)
(2, 1, +1, -½), (2, 1, +1, +½)
Differentiating Electron: last entering electron

- for C: (2, 1, 0, -½)
paramagnetic - if an atom has an unpaired electron

diamagnetic - if there are no unpaired electrons
Shortcut: Using noble gases

Mn: [Ar]4s23d5
Valence electrons - electrons occupying the outermost energy level

C: 5 e-
Examples:
7
N: 1s22s22p3

2p: ↓_ ↓_ ↓_
2s: ↓↑
Differentiating Electron: (2, 1, +1, -½) Valence Electrons: 5
8
2
O: 1s 2s 2p
2 4

2p: ↓↑ ↓_ ↓_
2s: ↓↑
25
Mn: 1s22s22p63s23p64s23d5
Ground state:
1s: ↓↑ 2s: ↓↑ 2p: ↓↑ ↓↑ ↓↑ 3s: ↓↑ 3p: ↓↑ ↓↑ ↓↑ 4s: ↓↑ 3d: ↓_ ↓_ ↓_ ↓_ ↓_
51
Sb: 1s 2
2s 2
2p6
3s 2
3p6
4s 2
3d10
4p6
5s 2
4d10
5p3
= [Kr]5s2
4d105p3
Ta: 1s22s22p63s23p64s23d104p65s24d105p66s24p145d3 = [Xe]6s24p145d3

73
Differentiating Electron: (5, 2, 0, -½) Valence Electrons: 2
Sr: 1s22s22p63s23p64s23d104p65s2= [Kr]5s2

38
Differentiating Electron: (5, 0, 0, +½) Valence Electrons: 2
Given: Differentiating Elctron: (4, 1, 0, +½)

Answer: 1s22s22p63s23p64s23d104p5 = [Ar]4s23d104p5 = Bromine
Stability
- if an atom has no incompletely filled orbitals, then it is stable
- completely filled > half filled > random incompletely filled
- exceptions in AUFBAU principle because of this
18
Ar: [He]2p63s23p6 3p: ↓↑ ↓↑ ↓↑ (Stable)
15
P: [He]2p63s23p3 3p: ↓_ ↓_ ↓_
16
S: [He]2p63s23p4 3p: ↓↑ ↓_ ↓_
Stability: Ar > P > S
Cu: [Ar]4s23d9
29
4s: ↓↑ 3d: ↓↑ ↓↑ ↓↑ ↓↑ ↓_ (LESS STABLE)
[Ar]4s13d10 4s: ↓_ 3d: ↓↑ ↓↑ ↓↑ ↓↑ ↓↑ (MORE STABLE)
Pseudo-Noble Gases
30
Zn: [Ar]4s23d10 - completely filled, a relatively stable element
- still less stable than a noble gas
30
Zn2+: [Ar]4s03d10 - psuedo noble gas ion
- also stable since all orbitals are filled
Fe: [Ar]4s23d6
26 26
Fe2+: [Ar]4s03d6
26Fe3+: [Ar]4s03d5 (most stable ion)
Cu: [Ar]4s13d10
29 29
Cu+: [Ar]4s03d10 (most stable ion)
29Cu2+: [Ar]4s03d9 (from 4s23d9)
The Periodic Table

Anton Laurent Lavosier
- tabulated 33 elements in his time
- only a simple table with no arrangement
Dalton's Chemical Symbols

- made symbols for 36 different elements
Dobereiner's Law of Triads

- groupings with three elements each
- based on similar chemical and physical properties
Newland's Law of Octaves

- arranged the elements into increasing atomic mass horizontally
- every 8th element would have same properties as the previous 8th
- new rows would start at the 8th element
Lothar Meyer
- observed similarities in properties in relation with atomic masses
Mendeleev and Meyer's Periodic Law

- the physical and chemical properties of elements are periodic functions of their atomic
weights
- discrepancies with elements such as K and Ar
- atomic weight is not the bast basis for arranging the elements
Moseley's Periodic Law

- the physical and chemical properties of elements are periodic functions of their atomic
numbers
- the modern periodic table is based from this
Location of Elements
- group no: column
- period no: row
- electron configuration can be used to tell the locations of elements
Old System
- Family A: Representative Elements
- if the differentiang electron occupies an s or p orbital
- group no: # of valence electrons
- period no: highest n value
- Family B: Transition Elements
- if the differentiating electron occupies a d or f orbital
- group no: # of electrons in ns + (n-1)d orbitals (roman numerals)
Examples:
25
Mn: [Ar]4s23d5 Family B Group No VIIB Period No 4
17
Cl: [Ne]3s23p5 Family A Group No VIIA Period No 3
IUPAC System
- groups numbered 1-18
- group No = no. of electrons in ns (s block)
= 10 + no of valence electrons (p block)
= no of electrons in ns + (n-1)d (d block)
Example:
15
P: [He]2p63s23p3 Group 15 Period 3
Periodicity of Properties
Periodic Properties
- mostly obsered at family A, the d and f blocks only differ in the inner electrons
Atomic Size/Radius
- one-half of the nuclear distance
⇓ : increasing size
- increase in n = higher number of energy levels
⇒ : decreasing size
- same energy level but increase in p+and e-
- higher electrostatic attraction
Ionization Potential/Energy
- amount of energy required to remove an electron from a neutral atom to convert it to a
positively charged ion
- 1st electron: 1st ionization potential, 2nd electron: 2nd ionization potential
⇓ : decreasing potential
- bigger atom = less attraction from nucleus, easier to remove
⇒ : increasing potential
- higher electrostatic atraction
Exceptions:
- Group 3 < 2
4
Be: 1s22s2 and 5B: 1s22s22p1

- since the electron at 2p is farther from the nucleus, it is easier to remove
- Group 6 < 5
7
Be: 1s22s22p3 and 8B: 1s22s22p4

- N is already stable and there is an e- - e- repulsion that decreases IP
- noble gases have high IP because of stability
Electron Affinity
- amount of enegry released when a neutral atom accepts an electron in its outermost shell
to becme a negatively charged ion
- it is expected to have a negative value
⇓ : decreasing affinity
⇒ : increasing affinity
- metals have less negative electron affinity while nonmetals have more negative ones
Electronegativity
- the tendency of an atom to attract electons to itself when it is chemically combined to
another atom
⇓ : decreasing electronegativity
⇒ : increasing electronegativity
- group VIIA/17 (halogens) have high electronagavity values (F = highest)
- noble gases do not need to attract electrons because they are stable
Effective Nuclear Charge

- the positive charge that electrons actually experience
- 4Be (1s22s2) has a +4 charge
- the electrons in 1s experience a +4 charge
- the electrons in 2s do not actually experience a +4 charge because of shielding
- the 1s electrons experience a +4 charge while the 2s electrons experience a
+2 charge
- 5B: 1s22s22p1
- 1s = +5, 2s = +3, 2p = +1
- this is the reason why the electron in the outermost level is the easiest to remove
- electrons in the same orbital cannot shield each other
The Chemical Bond

- result of the atomic quest for stability
- products have the same electron configuration as noble gases
- He: 1s2, others: ns2 np6 (stable octet)
Ionic or Electrovalent Bond

- electron transfer: metal/metalloid + nonmetal
- metal(cation): low ionization potential; nonmetal(anion): high electron affinity
- due to electrostatic attraction
- forms an ionic bond
- electronegativity difference > 1.7
ex.
11
Na: 1s22s22p63s1 (attains stability by losing one electron)
⇒ Na+: 1s22s22p6 (isoelectronic with Ne)
17
Cl: [Ne]3s23p5 ⇒ Cl-: [Ne]3s23p6
48
Cd: [Kr]5s 3d
2 10
⇒ Cd2+:[Kr]5s03d10 (pseudo-noble gas ion)
p/e ratio - determines the trend of size between elements and their ions
- higher p/e = smaller size
- lower p/e = bigger size
- the atom shrinks because of increased attraction of electrons to protons

#p #e p/e
Fe 26 26 1
Fe2+ 26 24 1.08
Fe 3+
26 23 1.13
Fe > Fe2+ > Fe3+
#p #e p/e #p #e p/e
Na+ 11 10 1.1 N3- 7 10 0.7
Mg 2+
12 10 1.2 O2-
8 10 0.8
Al3+ 13 10 1.3 F- 9 10 0.9
Na+ > Mg2+ > Al3+ N3->O2->F-
The Covalent Bond

- between nonmetals, neutral particles/molecules
- overlapping of orbitals must occur before electron sharing
- forming molecular orbitals
- head-on overlap: forms a sigma molecular orbital/bond
- occurs on s+s, px+px, hybrid orbitals
- lateral overlap: sideways, forms a pi molecular orbital/bond
- py+py, pz+pz
- creates a node at the center of the bond
Polarity
- nonpolar covalent bond (ex. H2)
- forms between similar atoms
- equal electron sharing
- EN difference ≤ 0.4
- polar covalent bond (ex. C-H)
- forms between dissimilar atoms
- unequal sharing of electrons
- EN difference from 0.4 to 1.7
- creates a dipole moment
- pointed to the more electronegative atom
Covalency No. - number of bonds that the atom has form with other atoms
- may be regardless of normal covalency number
Normal Covalency No.

- maximum number of covalent bonds that an atom can form
- CN = 8 - No. of valence electrons
Examples:
C: 8-4=4
O: 8-6=2
N: 8-5=3
Coordinate Covalent Bond

- a bond between two atoms in which the shared electrons come from one atom
Formal Charge = Group No. - (No. of unshared electrons + No. of bonds)
Lewis Dot Structure

Steps: (ex: NCl3)
1. No. of valence electrons needed
N: 1x8 = 8
Cl: 3x8 = 24

TOTAL: 32 valence electrons
2. No. of valence electrons available
N: 1x5 = 5
Cl: 3x7 = 21
3. No. of shared electrons: 32-26 = 6 electrons
4. No. of bonds: 6/2 = 3 bonds
Formal Charges:
FCN: 5-3-2 = 0 FCCl: 7-1-6 = 0
Central atom: highest covalency number
NH4+
N: 1x8 = 8
H: 4x2 = 8
N: 1x5 = 5
H: 4x1 = 4
TOTAL: 9 valence electrons - 1 electron(from charge) = 8 electrons
Formal Charges:
FCN: 5-4-0 = +1 FCH: 1-1-0 = 0
CO2
C: 1x8 = 8
O: 2x8 = 16
C: 1x4 = 4
O: 2x6 = 12
Formal Charges:
FCC: 4-4-0 = 0 FCO: 6-4-2 = 0
CO32-
C: 1x8 = 8
O: 3x8 = 24
C: 1x4 = 4
O: 3x6 = 18
TOTAL: 22 valence electrons + 2 = 24
Formal Charges:
FCC: 4-4-0 = 0 FCO1: 6-4-2 = 0 FCO2: 6-6-1 = -1
Contributing Structures based on Formal Charges

- structures with small formal charges (+2, -2, or less) are more likely
- formal charges of opposite signs are usually adjacent to each other
- highly electronegative atoms should have negative rather than positive formal charges
- most stable structures have the largest sum of the EN differences for adjacent atoms
- ones with fewer formal charges are more stable
Resonance Structures - different lewis structures for the same compound

- connected by the same framework of sigma bonds
FNO2
F: 1x8 = 8
N: 1x8 = 8
O: 1x8 = 8
F: 1x7 = 7
N: 1x5 = 5
O: 1x6 = 6
Structure 1: Double bond to O1

FCF: 0 FCN: +1 FCO1: 0 FCO2: -1
Structure 2: Double bond to O2
FCF: 0 FCN: +1 FCO1: -1 FCO2: 0
Structure 3: Double bond to F
FCF: +1 FCN: +1 FCO1: -1 FCO2: -1
- the third structure is not contributing because

- F, which is the most electronegative has a positive formal charge
- adjacent atoms have charges of the same sign
SCN-
S: 1x8 = 8
C: 1x8 = 8
N: 1x8 = 8
S: 1x6 = 6
C: 1x4 = 4
N: 1x5 = 5
TOTAL: 15 valence electrons + 1 = 16 electrons
Structure 1: Double bond to both S and N

FCs: 6-4-2 = 0 FCc: 4-4-0 = 0 FCN: 5-4-2 = -1
Structure 2: Triple bond to S
FCs: 6-2-3 = +1 FCc: 4-4-0 = 0 FCN: 5-6-1 = -2
Structure 3: Triple bond to N
FCs: 6-6-1 = -1 FCc: 4-4-0 = 0 FCN: 5-2-3 = 0
- structure 2 is the least contributing among the structures
Exceptions to the Octet Rule

1. Molecules with an odd number of electrons
ex: NO2
1. No. of valence electrons needed: 24 valence electrons
2. No. of valence electrons available: 17 valence electrons
4. No. of bonds: 7/2 = 3.5 bonds
- the resulting structure will have a lone electron

- compounds with odd numbers of electrons are called free radicals
2. Needs less than an octet to be stable

ex: BF3
- following to octet rule there will be the following formal charges
FCB: 3-4-0 = -1 FCF1: 7-1-6 = 0 FCF2: 7-1-6 = 0 FCF3: 7-2-4 = +1
- to remove the formal charges, B should only have 3 bonds to it
- BF3 then is very reactive and a Lewis acid
3. Expanded octet - only for elements at period 3 and below

ex: PCl5 - 5 bonds attached to P
ICl4- - 3 bonds and 2 lone pairs attached to I
- to expand an octet, remove the formal charge by adding bonds to the central atom
SNF3
FCS: 6-4-0 = +2 FCN: 5-1-6 = -2
- by adding two more S-N bonds, you can remove the formal charges
HClO4
FCCl: 7-4-0 = +3 FCO: 6-1-6 = -1
- by adding a Cl-O bond to each oxygen except the one bonded to H, you remove
the formal charges
Molecular Geometry (VSEPR Theory)

- based on bonding and nonbonding electrons (valence e-)
- search for the geometry with the most minimized electron repulsion between atoms
- repulsion: lone e- pair-lone e- pair > lone e- pair-bonding > bonding-bonding
hybridization - mixing of two ro more nonequivalnt atomic orbitals to for a new set of
equivalent degenerate orbitals
1. HgCl2
80
Hg: [Xe]6s24f145d10
GS: 6s: ↓↑ ES: 6s: ↓_ 6p: ↓_ __ __
HS: sp: ↓_ ↓_ (forms 2 covalent bonds)
sp: ↓↑Cl ↓↑Cl LINEAR molecular geometry

bond angle: 180º
2. BF3
5
B: 1s22s22p1
GS: 2s: ↓↑ 2p: ↓_ __ __ ES: 2s: ↓_ 2p: ↓_ ↓_ __
HS: sp2: ↓_ ↓_ ↓_ (forms 3 covalent bonds)
sp2: ↓↑F ↓↑F ↓↑F TRIGONAL PLANAR molecular geometry

bond angle: 120º
3. CH4
6
C: 1s22s22p2
GS: 2s: ↓↑ 2p: ↓_ ↓_ __ ES: 2s: ↓_ 2p: ↓_ ↓_ ↓_
HS: sp3: ↓_ ↓_ ↓_ ↓_ (forms 4 covalent bonds)
sp3: ↓↑H ↓↑H ↓↑H ↓↑H TETRAHEDRAL molecular geometry

bond angle: 109.5º
4. PCl5
15
P: [Ne]3s23p3
GS: 3s: ↓↑ 3p: ↓_ ↓_ ↓_ ES: 3s: ↓_ 3p: ↓_ ↓_ ↓_ 3d: ↓_ __ __ __ __
HS: sp3d: ↓_ ↓_ ↓_ ↓_ ↓_ (forms 5 covalent bonds)
sp3d: ↓↑Cl ↓↑Cl ↓↑Cl ↓↑Cl ↓↑Cl TRIGONAL BIPYRAMIDAL molecular geometry

bond angle: 120º (equatorial) 90º (axial)
5. SF6
16
S: [Ne]3s23p4
GS: 3s: ↓↑ 3p: ↓↑ ↓_ ↓_ ES: 3s: ↓_ 3p: ↓_ ↓_ ↓_ 3d: ↓_ ↓_ __ __ __
HS: sp3d2:↓_ ↓_ ↓_ ↓_ ↓_ ↓_ (forms 6 covalent bonds)
sp3d2: ↓↑F ↓↑F ↓↑F↓↑F ↓↑F ↓↑F OCTAHEDRAL molecular geometry

bond angle: 90º
Geometries with nonbonding electrons

6. NH3
7
N: 1s22s22p3
GS: 2s: ↓↑ 2p: ↓_ ↓_ ↓_
HS: sp3: ↓↑ ↓_ ↓_ ↓_ (forms 3 covalent bonds and 1 lone pair)
sp3: ↓↑ ↓↑H ↓↑H ↓↑H TRIGONAL PYRAMIDAL molecular geometry

bond angle: <109.5º (≈ 107) or TRIPOD
7. H2O
8
O: 1s22s22p4
GS: 2s: ↓↑ 2p: ↓↑ ↓_ ↓_
HS: sp3: ↓↑ ↓↑ ↓_ ↓_ (forms 2 covalent bonds and 2 lone pairs)
sp3: ↓↑ ↓↑ ↓↑H ↓↑H BENT or V-SHAPED molecular geometry

bond angle: <104.5º
8. SF4
16
S: [Ne]3s23p4
GS: 3s: ↓↑ 3p: ↓↑ ↓_ ↓_ ES: 3s: ↓↑ 3p: ↓_ ↓_ ↓_ 3d: ↓_ __ __ __ __
HS: sp3d: ↓↑ ↓_ ↓_ ↓_ ↓_ (forms 4 covalent bonds and 1 lone pair)
sp3d: ↓↑ ↓↑F ↓↑F ↓↑F ↓↑F DISTORTED TETRAHEDRON molecular geometry

or SEESAW
- lone pair will be found on the equatorial plane to minimize electron repulsion
9. ClF3
17
Cl: [Ne]3s23p5
GS: 3s: ↓↑ 3p: ↓↑ ↓↑ ↓_ ES: 3s: ↓↑ 3p: ↓↑ ↓_ ↓_ 3d: ↓_ __ __ __ __
HS: sp3d: ↓↑ ↓↑ ↓_ ↓_ ↓_ (forms 3 covalent bonds and 2 lone pairs)
sp3d: ↓↑ ↓↑ ↓↑F ↓↑F ↓↑F T-SHAPED molecular geometry

- lone pairs will be found on the equatorial plane to minimize electron repulsion
10. XeF2
54
Xe: [Kr]5s24d105p6
GS: 5s: ↓↑ 5p: ↓↑ ↓↑ ↓↑ ES: 5s: ↓↑ 5p: ↓↑ ↓↑ ↓_ 5d: ↓_ __ __ __ __
HS: sp3d: ↓↑ ↓↑ ↓↑ ↓_ ↓_ (forms 2 covalent bonds and 3 lone pairs)
sp3d: ↓↑ ↓↑ ↓↑ ↓↑F ↓↑F LINEAR molecular geometry

- lone pairs will be found on the equatorial plane to minimize electron repulsion
11. BrF5
35
Br: [Ar]4s23d104p5
GS: 4s: ↓↑ 4p: ↓↑ ↓↑ ↓_ ES: 4s: ↓↑ 4p: ↓_ ↓_ ↓_ 4d: ↓_ ↓_ __ __ __
HS: sp3d2:↓↑ ↓_ ↓_ ↓_ ↓_ ↓_ (forms 5 covalent bonds and 1 lone pair)
sp3d2: ↓↑ ↓↑F ↓↑F↓↑F ↓↑F ↓↑F SQUARE PYRAMIDAL molecular geometry

12. XeF4
54
Xe: [Kr]5s24d105p6
GS: 5s: ↓↑ 5p: ↓↑ ↓↑ ↓↑ ES: 5s: ↓↑ 4p: ↓↑ ↓_ ↓_ 5d: ↓_ ↓_ __ __ __
HS: sp3d2:↓↑ ↓↑ ↓_ ↓_ ↓_ ↓_(forms 4 covalent bonds and 2 lone pairs)
sp3d2: ↓↑ ↓↑ ↓↑F↓↑F ↓↑F ↓↑F SQUARE PLANAR molecular geometry
# e- pairs hybrid. # bonding # nonbonding geometry example

2 sp 2 0 linear HgO2, CO2
3 0 trigonal planar BF3
3 sp2
2 1 bent (v-shaped) NO2-
4 0 tetrahedral ICH4
4 sp3 3 1 trigonal pyramid NH2
2 2 bent (v-shaped) H2O
5 0 trigonal bipyr. PCl5
4 1 seesaw SF4
5 sp3d
3 2 t-shaped ClF3
2 3 linear XeF2
6 0 octahedral SF6
6 sp d
3 2
5 1 square pyramid BrCl5
4 2 square planar XeF4
Properties of Covalent Bonds

1. Bond polarity
- nonpolar bond: EN difference ≤ 0.4
- polar bond: 0.4 ≤ EN difference ≤ 1.7
- ionic bond: 1.7 ≤ EN difference
ex: H-F > H-Cl > H-Br > H-I (decreasing pattern)
2. Bond dissociation energy - energy meeded to destroy a covalent bond

↑ bond polarity ↑ bond dissociation energy
3. Bond order - number of bonds present between two atoms

↑ bond order ↑ bond dissociation energy
4. Bond length - internuclear distance

↑ size of atom ↑ bond length
↑ bond polarity ↓ bond length
5. Bond angle
- becomes smaller due to the presence of lone pairs
- deviations from the normal value
- comparing different bond angles
- difference in central atom ↑ size of central ↓ bond angle formed
- difference in ligand atoms ↑ size of ligand ↑ bond angle formed
Theories on Covalent Bonds

in C2H4: All H in s orbitals and all C are sp2 hybridized

C: GS: 2s: ↓↑ 2p: ↓_ ↓_ __ ES: 2s: ↓_ 2p: ↓_ ↓_ ↓_

HS: sp2: ↓_ ↓_ ↓_ 2p: ↓_
C-C bond: 4 C-H bonds:

1 sigma bond: sp2 - sp2 1 sigma bond: sp2 - s
1 pi bond: p-p
single bond - sigma bonds 1 sigma bond - sp2 - sp2

double bond - pi bonds 1 pi bond - p - p
- only unhybridized p orbitals can form pi bonds
in C2H2: All H in s orbitals and all C are sp hybridized
C: HS: sp: ↓_ ↓_ 2p: ↓_ ↓_
C-C bond: 2 C-H bonds:

1 sigma bond: sp - sp 1 sigma bond: sp - s
1 pi bond: py - py
1 pi bond: pz - pz
For N and O: the atom follows the hybridization of an adjacent carbon atom if one is present
- the unhybridized p orbital is almost always used as an orbital for pi bonds

- the exceptions are with compounds such as aniline, where there are adjacent C
and N molecules in which due to N following the hybridization of C, forms
an unhybridized p orbital not used for bonding (used for lone pairs) this N atom
has no pi bonds around it and the electrons in its lone pair is able to delocalize
delocalization - movement of pi electrons/lone pairs
polycentric molecular orbital

- is obtained by having pi electrons delocalize around the atom continuously in loops
(continuous delocalization)
Molecular Orbital Theory

- scope only on homonuclear diatomic atoms (H2, O2, etc)
- bonding molecular orbital - result of constructive overlap of molecular orbitals
- antibonding molecular orbital - result of destructive overlap of molecular orbitals
2 possible results of orbital overlapping

- s orbitals: σ bonding and σ antibonding (σ*) MO
- p orbitals: σ bonding, σ antibonding (σ*), p bonding, p antibonding (p*) MO
Molecular Orbital Energy Diagram

1. No. of MO formed = No. of atomic orbitals combined
2. Bonding MO will have a lower energy than the original atomic orbital while the antibonding
MO will have a higher energy than the original atomic orbital
3. The magnitude of decrease of energy for the bonding MO is equal to the magnitude of
increase of the antibonding MO
Bond Order = ½(# e- in BMO - # e- in ABMO)
- you can also determine if the molecule is paramagnetic or diamagnetic

O2, F2, Ne2 B2, C2, N2
σ*: __ σ*: __
p*: __ __ p*: __ __
2p 2p 2p 2p
INCREASING ENERGY
p: __ __ σ: __
σ: __ p: __ __
σ*: __ σ*: __
2s 2s 2s 2s
σ: __ σ: __
σ*: __ σ*: __
1s 1s 1s 1s
σ: __ σ: __
Changes in Matter
Chemical Changes
The Mole Concept
Formula Mass/Weight - refers to the mas of ionic compounds
Molecular mass/Weight - refers to covalent compounds
- both are computed by the summation of the atomic weights of the component elements
FW of KCl = AW K + AW Cl
= 39.098 + 25.45
= 74.55 amu
MW of C6 H12 O6 : C : 6 × 12.01 = 72.06

H : 12 × 1.01 = 12.12
O : 6 × 16.00 = 96.00
= 180.18 amu
FW of Ca3 (P O4 )2 : Ca : 3 × 40.01 = 120.03

P : 2 × 30.97 = 61.94
O : 8 × 16.00 = 128.00
= 309.97 amu
Mole
- amount of substance that contains as many elementary particles as there are atoms in 12 g
of 12C
- 1 mole = 6.022145x1023 particles = NA (Avogadro's Number)
- symbolizes a collection of particles (like dozen, etc.)
- of you collect one mole of atoms, its weight is equal to its atomic mass
- molar mass: weight of 1 mol of a substance
# of particles -> ÷ -> Moles -> x -> Mass in g

Avogadro's Number Molar Mass
# of particles <- x <- Moles <- ÷ <- Mass in g

Examples:
Needed: atoms in 4.21 mol of Pt

6.02 × 1023 atoms P t
(4.21 mol P t) = 2.53 × 1024 atoms
1 mol P t
Needed: molecules in 0.286 mol CH4

6.02 × 1023 molecules CH4
(0.286 mol CH4 ) = 1.72 × 1023 molecules CH4
1 mol CH4
same number of C atoms, multiply by 4 for number of H atoms
Needed: formula units in 0.50 mol KBr

6.02 × 1023 f ormula units KBr
(0.50 mol KBr) = 3.01 × 1023 f ormula units KBr
1 mol KBr
ionic compounds exist in a crystal lattice while covalent compounds exist as molecules
Needed: moles in 6.07g of CH4

M W : C : 12.01 + H : 4.04 = 16.05 g/mol

1 mol CH4
(6.07g CH4 ) = 0.38 mol CH4
16.05g CH4
Needed: moles in 198g of CHCl3

M W : C : 12.01 + H : 1.01 + Cl : 35.45 × 3 = 119.37 g/mol

1 mol CHCl3
(198g CHCl3 ) = 1.66 mol CHCl3
119.37g CHCl3
Needed: atoms of H in 25.6g of (N H2 )2 CO

1 mol (N H2 )2 CO 6.02 × 1023 molecules (N H2 )2 CO 4 atoms H
(25.6g (N H2 )2 CO)
60.06g (N H2 )2 CO 1 mol (N H2 )2 CO 1 molecule (N H2 )2 CO
= 1.02 × 1024 atoms H
Needed: grams of 3.14x1019 molecules of HCN

1 mol HCN 27.03g HCN
(3.14x1019 molecules HCN ) = 1.41 × 10−3 g HCN
6.02 × 1023 molecules HCN 1 mol HCN
Percent Composition
- percent by mass of each element in a compound
(molar mass)(no. of moles)

mass% =
(mass of compound)
N aN O3 : 22.99 + 14.01 + 3 × 16.00 = 85.00 g/mol

22.99
%N a : × 100 = 27.05% N a
85.00
14.01
%N : × 100 = 16.48% N
85.00
3 × 16.00
%O : × 100 = 56.47% O
85.00
H2 SO4 : 2 × 1.01 + 32.07 + 4 × 16.00 = 98.09 g/mol

2 × 1.01
%H : × 100 = 2.06% H
98.09
32.07
%S : × 100 = 32.69% S
98.09
4 × 16.00
%O : × 100 = 65.25% O
98.09

C18 H36 O2 : 12 × 12.01 + 36 × 1.01 + 2 × 16.00 = 284.54 g/mol
12 × 12.01
%C : × 100 = 75.98% C
284.54
36 × 1.01
%H : × 100 = 12.78% H
284.54
2 × 16.00
%O : × 100 = 11.25% O
284.54
Needed: g Al in 371g Al2 O3

Al2 O3 : 2 × 26.98 + 3 × 16.00 = 101.96 g/mol
2 × 26.98
%Al : × 100 = 52.92% Al
101.96
(371g Al2 O3 )(0.5292) = 196.33g Al
Empirical and Molecular Formula

Empirical Formula
- formula that is determined experimentally
- lowest integer form (simplest)
Given: 0.540g S and 0.538g O

1 mol S
mol S : (0.540g S) = 0.017 mol S ÷ 0.017 = 1
32.07g S

1 mol O
mol O : (0.538g O) = 0.034 mol O ÷ 0.017 = 2
16.00g O
Empirical F ormula : SO2
Empirical Formula based on % Composition
Given: 40.96%C 4.58%H 54.50%O

Basis: 100g

1 mol C
mol C : (40.92g C) = 3.41 mol C ÷ 3.41 = 1 × 3 = 3
12.01g C

1 mol H
mol H : (4.58g H) = 4.53 mol H ÷ 3.41 = 1.33 × 3 = 4
1.01 H

1 mol O
mol O : (54.50g O) = 3.41 mol O ÷ 3.41 = 1 × 3 = 3
16.00g O
Empirical F ormula : C3 H4 O3
Given: 24.75%K 34.77%Mn 40.51%O

Basis: 100g

1 mol K
mol K : (24.75g K) = 0.633 mol K ÷ 0.633 = 1
39.10g K

1 mol M n
mol M n : (34.77g M n) = 0.633 mol M n ÷ 0.633 = 1
59.94 M n

1 mol O
mol O : (40.51g O) = 2.53 mol O ÷ 0.633 = 4
16.00g O
Empirical F ormula : KM nO4
Experimental Determination (Combustion Analysis)

- CO2 produced: C content - H2O produced: H content

Given: f rom 11.5g ethanol, 22.0g CO2 and 13.5g H2 O produced

1 mol CO2 1 mol C
mol C : (22.0g CO2 ) = 0.500 mol C ÷ 0.25 = 2
44.02g CO2 1 mol CO2

1 mol H2 O 2 mol H
mol H : (13.5g H2 O) = 1.498 mol H ÷ 0.25 = 6
18.02g H2 O 1 mol H2 O

12.01 g C
g C : (0.500 mol C) = 6.005g C
1 mol C

1.01 g H
g H : (1.498 mol H) = 1.513g H
1 mol H
g O : 11.5 − 6.005 − 1.513 = 3.998g O

1 mol O
mol C : (3.998g O) = 0.25 mol C ÷ 0.25 = 1
16.00 O
Empirical F ormula : C2 H6 O
Molecular Formula
1. Determine the molar mass of the empirical formula (EW)
2. Find the ratio of the molar mass of the compound to the molar mass of the empirical
formula (factor = MW/EW)
3. Determine the number of units in the empirical formula of the compound
Examples
1. Given: EF : CH2 O M M : 60g/mol
CH2 O : 12.01 + 2.02 + 16.00 = 30.03g/mol
20
f= ≈2
30.03
M F : (CH2 O)2 or C2 H4 O2
2. Given: 14.6%C 39.0%O 46.3%F M M : 82g/mol

basis : 100g

1mol
146gC = 1.217molC ÷ 1.217 = 1
12.01gC

1mol
390gO = 2.438molO ÷ 1.217 = 2
16.00gO

1mol
463gF = 2.437molF ÷ 1.217 = 2
19.00gF
EF : CO2 F2
CO2 F2 : 12.01 + (2 × 16.00) + (2 × 19.00) = 82.01g/mol
82
f= ≈1
82.01
M F : CO2 F2
Stoichiometry
- calculations involving balanced chemical reactions
Recipe: balanced chemical reaction

Example: 2Na + Cl2 ⇒ 2NaCl (2mol Na + 1mol Cl2 ⇒ 2mol NaCl)

1. Given: 2H2 + O2 → 2H2 O
Moles of reactants needed? 2 molH2 and 1 molO2
Moles of reactants needed to produce 4 moles of H2 O? 4 molH2 and 2 molO2
Moles of hydrogen needed and water produced from 3 moles of oxygen?

2 molH2
3 molO2 = 6 molH2
1 molO2

2 molH2 O
3 molO2 = 6 molH2 O
1 molO2
Mole-Mole Conversions
1. Given: 2N a + Cl2 → 2N aCl 2.6 molCl2

2 molN aCl
2.6 molCl2 = 5.2 molN aCl
1 molCl2
2. Given: 4N H3 + 5O2 → 4N O + 6H2 O || 25.00 molN H3

5 molO2
molO2 = 25.00 molN H3 = 31.25 molO2
4 molN H3

4 molN O
molN O = 25.00 molN H3 = 25.00 molN O
4 molN H3

6 molH2 O
molH2 O = 25.00 molN H3 = 37.5 molH2 O
4 molN H3
Mole-Mass Conversions
1. Given: 2N a + Cl2 → 2N aCl || 5 molN a

1 molCl2 70.90 gCl2
gCl2 = 5.00 molN a = 177.25 gCl2
5 molN a 1 molCl2
2. Given: CoCl2 + HF → CoF2 + 2HCl || 15 molCoF2

1 molCoCl2 129.84 gCoCl2
gCoCl2 = 15.00 molCoF2 = 1947.6 gCoCl2
1 molCoF2 1 molCoCl2

2 molHF 20.01 gHF
gHF = 15.00 molCoF2 = 600.3 gHF
1 molCoF2 1 molHF
Mass-Mole Conversions
1. Given: 2C2 H6 + 7O2 → 4CO2 + 6H2 0 || 10.0 gH2 O

1 molH2 O 2 molC2 H6
molC2 H6 = 10.0 gH2 O = 0.185 molC2 H6
18.02 gH2 O 6 molH2 O
2. Given: CH4 + 2O2 → CO2 + 2H2 O || 24.0 gCH4

1 molCH4 2 molO2
molO2 = 24.0 gCH4 = 2.99 molO2
16.05 gCH4 1 molCH4
Mass-Mass Conversions
1. Given: N2 + 3H2 → 2N H3 || 2.00 gN2

1 molN2 2 molN H3 17.04 gN H3
gN H3 = 2.00 gN2 = 2.43 gN H3
28.02 gN2 1 molN2 1 molN H3
2. Given: 2N a + I2 → 2N aI || 93.25 gI2

1 molI2 2 molN aI 149.89 gN aI
gN aI = 93.25 gI2 = 110.14 gN aI
253.8 gI2 1 molI2 1 molN aI

3. Given: 2KClO3 → 2KCl + 3O2 || 46.0 gKClO3

1 molKClO3 3 molO2 32.00 gO2
gO2 = 46.0 gKClO3 = 18.02 gO2
122.55 gKClO3 2 molKClO3 1 molO2
Excess Reactant
- said to be in excess (there is too much)
Limiting Reactant
- limits how much product we get. Once it runs out, the reaction stops
1. Given: 2Al + 3Cl2 → 2AlCl3 || 10.0 gAl || 35.00 gCl2

Limiting Reactant:

1 molAl 2 molAlCl3 133.33 gAlCl3
If Al: gAlCl3 = 10.0 gAl = 49.42 gAlCl3
26.98 gAl 2 molAl 1 molAlCl3

1 molCl2 2 molAlCl3 133.33 gAlCl3
If Cl: gAlCl3 = 35.00 gCl2 = 43.38 gAlCl3
70.9 gCl2 3 molCl2 1 molAlCl3
The LR is the reactant that produces less product, so in this reaction, Cl2 is the LR
and Al is in excess. The reaction produced 43.38 gAlCl3
Excess: (Law of Conservation of Mass)
35.0gAl + 10.0gCl2 = 45.0greactant − 43.48gproduct = 1.12gAl
2. Given: 2Al + F e2 O3 → Al2 O3 + 2F e|| 124 gAl || 601 gF e2 O3

a. Limiting Reactant:

1 molAl 1 molAl2 O3 101.96 gAl2 O3
If Al : gAl2 O3 = 124 gAl = 234.30 gAl2 O3
26.98 gAl 2 molAl 1 molAl2 O3

1 molF e2 O3 1 molAl2 O3 101.96 gAl2 O3
If F e2 O3 : gAl2 O3 = 601 gF e2 O3 = 383.71g
159.7 gF e2 O3 1 molF e2 O3 1 molAl2 O3
Al is the LR
The reaction produced 234.30 gAl2 O3
b. Excess:

1 molAl 1 molF e2 O3 159.7 gF e2 O3
gF e2 O3 = 124 gAl = 366.99 gF e2 O3
26.98 gAl 2 molAl 1 molF e2 O3
601gF e2 O3 − 366.99gF e2 O3 = 234.01gF e2 O3
Percent Yield
- the amount of product made in a chemical reaction
1. actual yield - experimental yield, what you got in the lab

2. theoretical yield - what the balanced equation tells what the yield should be

actual yield
% yield = × 100
theoretical yield
1. Given: 2Al + 3CuSO4 → Al2 (SO4 )3 + 3Cu || 3.92gAl produced 6.78gCu

a. actual yield: 6.78gCu
b. theoretical yield:

1 molAl 3 molCu 62.55 gCu
gCu = 3.92gAl = 13.85 gCu
26.98 gAl 2 molAl 1 molCu

6.78 gCu
c. % yield = × 100 = 48.95%
13.85 gCu

2. Given: T iCl4 + 2M g → T i + 2M gCl2 || actual yield: 7.91 × 106 gT i
3.54 × 107 gT iCl4 || 1.13 × 107 gM g
a. theoretical yield:

1 molT iCl4 1 molT i 47.87 gT i
gT i = 3.54 × 107 gT iCl4 = 8.93 × 106 gT i = LR
189.67 gT iCl4 1 molT iCl4 1 molT i

1 molM g 1 molT i 47.87 gT i
gT i = 1.13 × 107 gM g = 1.113 × 107 gT i
24.31 gM g 2 molM g 1 molT i

7.91 × 106 gT i
b. % yield = × 100 = 88.49%
8.93 × 106 gT i
3. Given: CaSO4 → CaO + SO3 || at 85% yield: 33.0 gCaSO4

136 gCaSO4 produces 80.07 gSO3
If 100 % complete: 33.0 gCaSO4 ÷ 0.85 = 38.82 gCaSO4
a. actual yield:

1 molCaSO4 1 molCaO 56.01 gCaO
gCaO = 38.82 gCaSO4 = 15.98 gCaO
196.15 gCaSO4 1 molCaSO4 1 molCaO

80.07 gSO3
b. gSO3 = 38.82 gCaSO4 = 22.83gSO3
136 gCaSO4
wt. pure
% purity = × 100
wt. unpure
4. Given: 2KN O3 → 2KN O2 + O2 || gO = 1.42gO2 || gKN O3 = 10gKN O3

1 molO2 2 molKN O3 101.11 gKN O3
gKN O3 = 1.42 gO2 = 8.97 gKN O3
32.00 gO2 1 molO2 1 molKN O3
8.97 g
% purity = × 100 = 89.7%
10.0 g
5. Given: 2C4 H10 + 13O2 → 8CO2 + 10H2 O

a. 1.0 kgC4 H10

1 molC4 H10 13 molO2 32.00 gO2 1 kgO2
kgO2 = 1000 gC4 H10 = 3.58 kgO2
58.14 gC4 H10 2 molC4 H10 1 molO2 1000 gO2
b. 89% yield
Unused O2 : 3.58 kgO2 − 89%
(3.58 kgO2 )(0.11) = 0.39 kgO2
c. 85% pureO2 || 1 kgO2

Unburned C4 H10 :
100% pureO2 :

1 molO2 2 molC4 H10 58.14 gC4 H10
kgC4 H10 = 1000 gO2 = 279.52 gC4 H10
32.00 gO2 13 molO2 1 molC4 H10
85% pureO2 :

1 molO2 2 molC4 H10 58.14 gC4 H10
kgC4 H10 = 850 gO2 = 237.59 gC4 H10
32.00 gO2 13 molO2 1 molC4 H10
Unburned C4 H10 = 279.52 − 237.59 = 41.93 gC4 H10
Nuclear Changes
Nuclear Chemistry
Nuclear vs. Chemical Change

Nuclear Change Chemical Change
involve the nucleus and inner electrons involve only valence electrons
nucleus opens and p+ and n0 rearrange valence electron transfer/sharing
elements transform into other elements rearrangement of atoms and bonds
needs/releases a high amount of energy needs/releases a small amount of energy
rates usually not affected by P, T, catalyst rates usually affected by P, T, catalyst
Radioactivity
- discovered by Marie Curie
- the spontaneous disintegration (ionizing radiation) of unstable elements into smaller pieces
- these elements that can do this are called radionuclides
Types of Radioactive Decay

4 4
1. Alpha Decay - Loss of an a-particle (a helium nucleus): 2 He or 2 α
- ↓ 2 n0 and ↓ 2 p+
238
92 U →234 4
90 T h +2 He
0 0
2. Beta Decay - Loss of a b-particle (a high energy electron): −1 e or −1 β
1 1 0
- ↓ 1 n0 and ↑ 1 p+ ( 0 n →1 p +−1 e )
131
53 I →131 0
54 Xe +−1 e
3. e+ emision - Loss of a positron (a particle that has the same mass as but opposite
0 0
charge than an electron): 1 e or 1 β
1 0 1
- ↑ 1 n0 and ↓ 1 p+ (1 p →1 β +0 n )
11
6 C →11 0
5 B +1 e
4. g emission - Loss of a g-ray (high-energy radiation that almost always accompanies the
0
loss of a nuclear particle): 0 γ
5. e- capture - Addition of an electron to a proton in the nucleus. As a result, a proton is

1 0 1
transformed into a neutron. 1 p +−1 e →0 n
- ↑ 1 n0 and ↓ 1 p+
37
18 Ar +0−1 e →37
17 Cl
Balancing Nuclear Reactions

1. Conserve Mass No.
2. Conserve atomic no./nuclear charge
Examples:
1. 212 P o : α decay 2. 60
Co : β decay
212
84 P o →42 He +208
82 P b 60
27 Co →0−1 e +60
28 N i
Neutron-proton ratios
- elements with more than one proton have repulsions between the protons in the nucleus
- a strong nuclear force helps keep the nucleus from flying apart
- Neutrons play a key role stabilizing the nucleus.

- For (Z ≤ 20) stable neutron-to-proton ratio is ≈ 1:1.
- larger nuclei takes a greater number of neutrons to stabilize the nucleus.
Stable Nuclei
- belt of stability shows what nuclides would be stable in certain ratios
- nuclei above this belt have too many neutrons -> tend to beta decay
- Z > 83 are unstable -> tend to alpha decay
Trends
Magic Numbers
Nuclei with 2, 8, 20, 28, 50, or 82 protons or tend to be more stable
2, 8, 20, 28, 50, 82, or 126 neutrons
Stability (protons-neutrons): even-even > even-odd ≈ odd-even > odd-odd
Radioactive Series
- Radioactive decay usually is not a one-step nuclear transformation.
- series of decays until they form a stable nuclide (often a nuclide of lead).
Half-Life
- time it takes for a substance to become 50% of its original mass
- constant and independent of initial composition
Mass Defect
MD = theoretical mass - actual mass
- some of the mass can be converted into energy (E=mc2) called
nuclear binding energy (BE)
- energy required to break up a nucleus into its component protons and neutrons.
Given: Mn0 = 1.00867 amu || Mp+ = 1.00728 amu || M60

27 Co
= 59.933819 amu
theoretical : (27p+ × 1.00728 amup+ ) + (33n0 × 1.00867 amun0 ) = 60.48267 amu
∆M = 60.48267 amu − 59.933819 amu = 0.548851 amu
Types of Nuclear Changes

- nucleus undergoes change as a result of bombardment by elementary particles/nuclei
Nuclear Fission
- a heavy nucleus dicides and form smaller nuclei
- followed by high amount of energy
Nuclear Chain Reaction

- starts with bombardment and splitting of a radioactive parent
- the neutron products bombard other possible nuclei
- continues until not enough radioactive nuclides are available (the chain reaction will die out)
- Critical Mass - minimum amount of fissionable material present for the chain reaction to
be sustained
- Supercritical Mass - too much mass that creates an uncontrolled accelerated process
that may explode
Nuclear Fusion
- combination of nuclei
- can occur only in very high temperatures (like at stars)
- not radioactive
- possible to perform in a Tokamak apparatus that uses magnetic fields to generate heat
Radiation on Matter

Does it pass through? Paper 0.5 cm lead 10 cm lead
alpha particle X X X
beta particle O X X
gamma ray O O X
Phases of Matter
Intermolecular Forces of Attraction
- forces of attractions that exist between molecules
- determine:
- state
- melting and boiling points
- solubilities
van der Waals or London dispersion forces

- weakest of the intermolecular forces
- due to uneven electron distributions in neighboring molecules
- weak attraction of the nuclei in a molecule for electrons in another
- attraction of the + side of a nonpolar molecule to the - side of another
- ↑ size (and ↑ electrons), ↑ LDF due to higher polarizability
- only type of IFA between nonpolar molecules, present in ALL molecules
- only temporary, due to temporary dipole moments
- induced dipole-induced dipole attraction
nonpolar molecules: µ total = 0

polar molecules: µ total = >0
CCl4 - nonpolar because there is a cancellation of dipole moments

- electrically neutral
Examples: H2, Cl2, CO2, CH4 (only held by LDF)
Dipole-Dipole Attractions
- molecules with permanent net dipoles (polar molecules)
- partial positive charge on one molecule is electrostatically attracted to the partial negative
charge of another
- stronger than LDF
Examples: SCl2 PCl3, CH3Cl
Hydrogen-Bond
- special dipole-dipole
- H atoms are attracted to F, O and N atoms
- stronger than dipole-dipole and LDF
volume contraction - occurs when you mix 50mL water and 50mL ethanol
Ion-Dipole Attraction
- attraction between an ion and a polar molecule
- accounts for the solubility of most ionic compounds in polar solvents
- the larger the charge the stronger the force
What type(s) of intermolecular forces exist between each of the following molecules?
HBr (polar): dipole-dipole, LDF
CH4 (nonpolar): LDF
SO2 (polar): dipole-dipole, LDF
Summary of IFAs: (strongest to weakest)

- ion-dipole (ion & polar molecule)
- H-bonding (N, O, F attached to H)
- dipole-dipole (polar molecules)
- ion-induced dipole (ion & nonpolar molecule)
- dipole-induced dipole (polar & nonpolar molecule)
- london dispersion forces/Van der Waals (nonpolar molecules)
Indicators of Strength of IFA

1. Molar Heat of Vaporization (Liquid-Gas)
- Heat energy required to evaporate one mole of a given substance at a given temperature
- ↑ IFA, ↑ ∆Hvap
Examples: CH4 < SO2 < H2O
2. Boiling Point
- vapor pressure = atmospheric pressure
- ↑ IFA, ↑ BPt
3. Vapor Pressure
- pressure exerted by a gas on a liquid in which it is in equilibrium
- ↑ volatility, ↑ VP, ↓ BPt
- ↑ IFA, ↓ VP
4. Molar Heat of Fusion (Solid-Liquid)

- heat energy required to melt one mole of a solid
- ↑ IFA, ↑ ∆Hfus
5. Melting Point
- temperature at which the liquid and solid phases coexist in equilibrium
- ↑ IFA, ↑ MPt
6. Viscosity
- measure of a fluid’s resistance to flow.
- measured in Nsm-2 (SI Units) or poise (P) or centipoise (cP)
- ↑ IFA, ↑ Viscosity
7. Surface Tension
- amount of energy required to stretch or increase the surface of a liquid by a unit area
- due to the unbalanced force experience by molecules at the surface of a liquid
- drops are spherical because the sphere offers the smallest area for a definite volume.
8. Solubility
- max amount of solute that will dissolve in a solvent at a given temperature
- ↑ interaction, ↑ solubility
Comparison of the Phases of Matter

- solid, liquid and gas
- interaction: Solid>Liquid>Gas
- gases - total disorder and freedom
- liquids - "gliding" movement on top of each other (flow)
- solids - vibrations
- shape and volume:
- solids - definite shape and volume
- liquids - indefinite shape, definite volume
- gases - indefinite shape and volume
- only gases are compressible
Phase Changes and Phase Diagrams

Molar Heat of Vaporization
- Heat energy required to evaporate one mole of a given substance at a given temperature
- Energy related to evaporation and condensation
+∆Hvap: evaporation (endothermic)
–∆Hvap: condensation (exothermic)
boiling point - vapor pressure = atmospheric pressure
normal boiling point - boiling point at 1 atm
Molar Heat of Fusion

- is the energy that must be absorbed to melt one mole of a substance
melting point/freezing point - the temperature at which the solid and liquid phases coexist
in equilibrium
Molar heat of sublimation - the energy required to sublime 1 mole of a solid

- ∆Hsub = ∆Hfus + ∆Hvap
Phase Diagram - a graphical way to summarize the conditions under which equilibrium
exist between the different states of matter. It allows us to predict the phase of a substance
that is stable at any given temperature and pressure
Triple Point: where all three phases are in equilibrium

Critical Point: point where critical Temp. and Pressure is achieved
Critical Temperature: highest temperature at which a distinct liquid phase can form
Critical Pressure: pressure required to bring about liquefaction at critical temperature
Supercritical fluid: fluid existing in critical temperatures
negative fusion slope of H2O: causes the lower density of ice than water
The Gaseous State

- gases are either monoatomic (Ne), diatomic (N2) or polyatomic (CH4)

1. have mass
2. compressible
3. fill containers
4. diffusible
5. exert pressure - force on a gas on container walls
Kinetic Molecular Theory

- attraction (IFA) vs. dispersion (KE)
- basis for Gas Laws
- predicts IDEAL GAS behavior
Postulate 1: Tiny particles in all matter are in constant motion

- constant random straight motion; collide against other molecules or container walls
- movement is changed by colliding
Postulate 2: Colliding is perfectly elastic
- kinetic energy of the system is preserved
Postulate 3: Molecular motion is greater at higher temperature.
Postulate 4: Volume of gas molecules is negligible compared to the total volume of the
container (Vgas<<Vcontainer)
- empty spaces are in between particles
Postulate 5: No attractive or repulsive force occur.
- negligible IFA
Gas Variables
1. n: amount of moles
- amount of gas
- 6.02x1023 particles/mol
2. V: volume
- assume Vgas ≈ Vcontainer
- SI unit: L (1L = 1dm3)
3. T: temperature
- average kinetic energy
- in Kelvin: K = Cº + 273
4. P: pressure
- exerted on the wall of the container
- atm, mmHg and torr
- 1 atm = 760 torr = 760 mmHg
Standard Temperature and Pressure

ST: 273K (0ºC) SP: 1 atm
- because the gas behavior varies in different T and P ranges
The Gas Laws

1
P ∝ k = T, n P1 V1 = P2 V2
Boyle's Law V P V = k
- the P vs V graph is logarithmic
1. Given: V1 = 0.55L || P1 = 1atm || P2 = 0.40atm || V2 =?

P1 V1 = P2 V2
P1 V1 (1 atm)(0.55 L)
V2 = = = 1.375 L
P2 0.40 atm
2. Given: V1 = 946mL || P1 = 726mmHg || V2 = 154mL || P2 =?

P1 V1 = P2 V2
P1 V1 (726 mmHg)(946 mL)
P2 = = = 4459.71 mmHg
V2 154 mL
V V1 V2
=k =
Charles' Law V ∝ T k = P, n T T1 T2
- the V vs T graph is linear
1. Given: V1 = 452mL || T1 = 295K || T2 = 460K || V2 =?

V1 V2
=
T1 T2
V1 T2 (452 mL)(460 K)
V2 = = = 704.81 mL
T1 295 K
2. Given: V1 = 3.20L || T1 = 398K || V2 = 1.54L || T2 =?

V1 V2
=
T1 T2
T 1 V2 (398 K)(1.54 L)
T2 = = = 191.54 K
V1 3.20 L
P P1 P2
=k =
Gay-Lussac's Law P ∝ T k = V, n T T1 T2
- the P vs T graph is linear
1. Given: P1 = 3.0atm || T1 = 400K || T2 = 500K || P2 =?

P1 P2
=
T1 T2
P1 T2 (3.0 atm)(500 K)
P2 = = = 3.75 atm
T1 400 K
Combined Gas Law

P1 V 1 P 2 V2
=
T1 T2

1. Given: T1 = 281K || P1 = 6.4atm || V1 = 2.1mL || T2 = 298K || P2 = 1atm || V2 =?
P1 V1 T2 (6.4 atm)(2.1 mL)(298 K)
V2 = = = 14.25 mL
T 1 P2 (281 K)(1 atm)
2. Given: V1 = 4.0L || P1 = 1.2atm || T1 = 339K || V2 = 1.7L || T2 = 315K || P2 =?

P 1 V1 T2 (1.2 atm)(4.0 L)(315 K)
P2 = = = 2.62 atm
T1 V2 (339 K)(1.7 L)
Ideal Gas Law

P V = nRT
Latm
R = 0.08206
molK
1. Given: n = 1.82mol || V = 5.43L || T = 342.5K || P =?

Latm
nRT (1.82 mol)(0.08206 molK )(342.5 K)
P = = = 9.42 atm
V (5.43 L)
2. Given: n = 2.12mol || P = 6.54atm || T = 349K || P =?

Latm
nRT (2.12 mol)(0.08206 molK )(349 K)
V = = = 9.28 L
P (6.54 atm)
Density Formula Molar Mass Formula

PM ρRT
ρ= M=
RT P
1. Given: P = 752mmHg || T = 328K || M MN H3 = 17.04g/mol || ρ =?

1 atm g
PM (752 mmHg) 760 mmHg (17.04 mol )
ρ= = Latm
= 0.63 g/L
RT (0.08206 molK )(328 K)
2. Given: P = 779mmHg || T = 335K || M MN H3 = 352.03g/mol || ρ =?

1 atm g
PM (779 mmHg) 760 mmHg (352.03 mol )
ρ= = Latm
= 13.13 g/L
RT (0.08206 molK )(335 K)
3. Given: P = 288atm || T = 309K || ρ = 7.71g/L || M M =?

ρRT (7.71 Lg )(0.08206 molK
Latm
)(309 K)
MM = = = 67.88 g/mol
P (288 atm)
Through trial and error (MM Cl: 35.45g/mol O: 16.00g/mol) the molecular formula is ClO2
4. Given: 33%Si 67%F || P = 1.20atm || T = 308K || V = 0.210L || mass = 2.38g

basis: 100g

1 molSi
molSi = 33gSi = 1.17 molSi ÷ 1.17 = 1
28.09 gSi

1 molF
molF = 67gF = 3.53 molF ÷ 1.17 = 3
19.00 gF
EF : SiF3
EW : 28.09 + (3 × 19) = 85.09 g/mol
Latm
ρRT gRT (2.38 g)(0.08206 molK )(308 K)
MM = = = = 168.5 g/mol
P VP (0.210 L)(1.20 atm)
168.5
f actor : ≈2
85.04
M F : Si2 F6

Avogadro's Law V ∝ n k = P, T 1mol = 22.4L at STP
(molar vol. of ideal gas at STP)
1. Given: 2C2 H2(g) + 5O2(g) → 4CO2(g) + 2H2 O(l) || VC2 H2 = 2.64LC2 H2

1 molC2 H2 5 molO2 22.4 LO2
VO2 = 2.64 LC2 H2 = 6.6 LO2
22.4 LC2 H2 2 molC2 H2 1 molO2
2. Given: 2C4 H10(g) + 13O2(g) 8CO2(g) → +10H2 O(l) || VC4 H10 = 14.9LC4 H10

1 molC4 H10 13 molO2 22.4 LO2
VO2 = 14.9 LC4 H10 = 96.85 LO2
22.4 LC4 H10 2 molC4 H10 1 molO2
3. Given: 2N aN3(s) → 2N a(s) + 3N2(g) || gN aN3 = 60gN aN3 || T = 294K || P = 823mmHg

 
Latm
1 molN aN3 3 molN2 (0.08206 molK )(294K)
VN2 = 160 gN aN3   = 30.74 LN2
65.02 gN aN3 2 molN aN3 (823mmHg) 1 atm
760 mmHg
4. Given: C6 H12 O6(s) + 6O2(g) → 6CO2(g) + 6H2 O(l) || gC6 H12 O6 = 5.60gC6 H12 O6
|| T = 310K || P = 1atm
Latm

1 molC6 H12 O6 6 molCO2 (0.08206 molK )(310K)
VCO2 = 5.60 gC6 H12 O6
180.18 gC6 H12 O6 1 molC6 H12 O6 (1atm)
= 4.74 LCO2
Dalton's Law of Partial Pressures

nn
Xn =
PT = PA + PB + PC + ... + Pn Pn = Xn PT nT
Ideal Behavior
- possible in ↑T and ↓P
- if n=1, then PV/RT = 1
Deviations from Ideal Behavior

- real gases have volume (ideal gases assume no volume)
- real gases have IFA
- will cause the pressure on the container wall to decrease
Van der Waals Equation for Real Gases

an2
P+ (V − nb) = nRT
V2

an2
P+ (V − nb) : correct V
: correct P
V2
a: correction due to IFA b: correction due to container walls
The Liquid State

Properties of a Liquid
- Liquids are almost incompressible, assume the shape but not the volume of container:
- Liquids molecules are held closer together than gas molecules, but not so rigidly that the
molecules cannot slide past each other.
1. Viscosity
- liquid’s resistance to flow due to IFA which impedes movement
- ↑ SA ↓ viscosity - ↑IFA ↑ viscosity - ↑ T ↓ viscosity
2. Surface Tension
- amount of energy required to increase the surface area of a liquid

- measure of the “cohesive force that must be overcome”
- liquid surfaces tend to have the smallest area (spherical)
- ↑ IFA ↑ Surface Tension
Example: Hg > water > ethanol
3. Capillarity/ Capillary Action

- rising of a liquid through a narrow space against the pull of gravity
Cohesive Force – binds molecules to each other (IFA)
Adhesive Force – binds molecules to a surface

meniscus - the shape of the liquid surface.
- adhesive forces > cohesive forces
- the liquid surface is attracted to its container more than the bulk
molecules. Therefore, the meniscus is U-shaped
Example: water
- cohesive forces > adhesive forces
- the meniscus is curved downwards
Example: mercury
The Solid State

Types of Solid
crystalline - solids with an ordered atomic arrangement
polycrystalline - solids with an many ordered atomic arrangements
amorphous - solids without an ordered atomic arrangement
Solutions
- homogenous mixtures
- solvent: the component with the higher amount (dissolver)
- solute: the component with the lower amount (dissolved)
- aqueous solution: water is the solvent
Examples: air, antifreeze in water, brass (and other alloys), soda, seawater
solid-solid are only called homogenous mixtures
The Dissolution Process

Solvation/Dissolution: the surrounding of solvent molecules to solute molecules
In ionic compounds:
- involves attraction of ions to positive and negative parts of the solvent.
- the solvent surrounds the ions
- ∆H changes
- IFA (ionic): ion-dipole
Polar Molecules
Example:
- CH3CH2OH is soluble in water due to formation of H-bonds
- sucrose is also soluble in water due to formation of H-bonds
Substances insoluble in water

- oil: oil is immiscible in water because they cannot form H-bonds and oil is nonpolar
- the water-water H-bonds are more stronger than the attraction of oil and water
Energy Changes in Solvation

1. Separation of Solute Particles (endothermic, +∆H)
2. Separation of Solvent Particles (endothermic, +∆H)
3. Formation of interaction between solute and solvent (exothermic -∆H)
In a Solution: sol-sol interaction > sol-sol and solv-solv interactions
Heat of Solution: ∆Hsoln = ∆Hsol-sol + ∆Hsolv-solv + ∆H sol-solv
Physical manifestation: exothermic: increase in temperature felt

endothermic: decrease in temperature felt
Entropy Changes in Solvation

1. Separation of Solute Particles (+∆S)
2. Separation of Solvent Particles (+∆S)
3. Formation of interaction between solute and solvent (-∆S)
In Total: +∆S in solvation
Factors Affecting Solubility

1. Nature of Solute/Solvent
- dependent on the polarity of solute and solvent
- "like dissolves like" (↑ IFA, ↑ solubility)
- polar sol, polar solv - nonpolar sol, nonpolar solv
- ↑ size, ↑ LDF, ↑ IFA, ↑ solubility
Example: C6H12 and glucose
- cyclohexane is nonpolar, it doesn't dissolve in water
- glucose is polar, it dissolves in water
- gases are slightly soluble in water ↑ solubility, ↑ mass
2. Pressure
- only affects gases ↑P, ↑ solubility Henry's Law: SG = kPG
3. Temperature
solid-liquid: ↑ T, ↑ solubility (endothermic) for salts
Cs2(SO4)3 : exothermic ↑ T, ↓ solubility
gas-liquid: ↑ T, ↓ solubility
4. Surface Area
↑ SA, ↑ Solubility
Dissolution vs. Chemical Reaction

- just because a solid disappears doesn't mean it was dissolved
- a chemical reaction may have occurred
- dissolution is a physical change while chemical reactions are chemical changes
- to check: remove the solvent - if there was remaining solid, it was dissolution
- if there was nothing remaining, it was a reaction
Solubility: the maximum amount of solute that can be dissolved in a solvent at a certain
temperature
Types of Solutions
Degree of Saturation
- qualitative description of concentration
1. saturated - holds as much solute as possible at a certain temperature
- the dissolved solute is in equilibrium with the undissolved solute
2. unsaturated - less than max amount of solute is held at a given temperature

3. supersaturated - solvent holds more than the normal possible amount
Concentration
Concentration Units
molsol gsol
Molarity (M) M= M=
- temperature dependent Lsoln (M Msol )(Lsoln )
Molality (m) molsol

m=
kgsolv
Normality (N) # equivalent weights N =M ×f

N=
Lsoln
# equivalent weights = molsol × f

Factor
1. Acids f = # of replaceable hydronium ion (H+)
Examples: HCl (f = 1) H2SO4 (f = 1, 2; diprotic acid) CH3COOH (f = 1)
Polyproptic acid - stepwise (one at a time) donation of H+

- If ionization equation is not given: assume max factor
H3 P O4 (triprotic)
H 3 P O 4 → H + + H2 P O 4 − : f = 1
H2 P O4 − → H + + HP O4 2− : f = 2
2−
HP O4 → H + + P O4 3− : f = 3
2. Bases f = # of replaceable OH-

Examples: NaOH (f = 1) Mg(OH)2 (f = 2, 1)
Al2(OH)3 (f = 1, 2, 3) NH3 (f = 1; NH4OH)
3. Salts f = total (+) charges or total (-) charges

Examples: NaCl (f = 1) MgO (f = 2)
Ca3(PO4)2 (f = 2)
4. Oxidizing Agents f = # of e- gained

Examples: acidic
M nO4 − −−−→ M n2+ : f = 5
basic/neutral
M nO4 − −−−−−−−−→ M nO2 : f = 3
5. Reducing Agents f = # of e- lost

2+ 3+
Examples: Fe → Fe : f = 1
gsol
Mass % %(w/w) = × 100
gsoln
gsol
%(w/v) = × 100
mLsoln
mLsol
%(v/v) = × 100
mLsoln

Proof Strength proof = 2 × % alcohol
Parts per Million (ppm) gsol

ppm = × 106
gsoln or mLsoln
mgsol
=
kgsoln or Lsoln
gsol
Parts per Billion (ppb) ppb = × 109
gsoln or mLsoln
µgsol
=
kgsoln or Lsoln
p-Scale p = −log[solute] (used if concentration is very low)
Mole Fraction nsol nsolv

χsol = χsolv =
nsoln nsoln
nsoln = nsol + nsolv Xsol + Xsolv = 1
Mole % χ × 100
Dilution
C 1 V 1 = C2 V2
Example:
Colligative Properties
- dependent only on the amount of particles present
non-electrolyte - does not dissociate in solution ex. 1M C6H12O6

electrolyte - dissociates in solution ex. 1M NaCl ⇒ Na+ + Cl-
For nonvolatile, non-electrolyte solutes:
1. Vapor Pressure Lowering

- due to solute particles on the surface
- also due to IFA that prevents vaporization of solvent
Pf = χsolv P ◦
∆P = χsol P ◦
2. Boiling Point Elevation 3. Freezing Point Depression

∆tb = mKb ∆tf = mKf
Kb (water) = 0.52◦ C/m Kf (water) = 1.86◦ C/m
m = molality m = molality
4. Osmotic Pressure
Osmosis
- movement of solvent to a high concentration of solvent to a low concentration of solvent
- movement of solvent to a low concentration of solute to a high concentration of solute
- passes through a semi-permeable layer that only allows solvent to pass through
Π = CRT C = molar concentration

Latm
R = 0.08206
molK
T = absolute temperature(K)

van't Hoff factor (i)
- considers amount of ionization of electrolyte solutes in solution
∆tb observed
i=
∆tb theoretical (nonelectrolyte) ex. NaCl (i = 2)
CaCl
∆tb observed 2
(i = 3)
=
mkb
For Electrolyte Solutes:
∆P = i(χsol P ◦ ) ∆tf = i(mKf )

∆tb = i(mKb ) Π = i(CRT )
Unless specified, we assume 100% ionization of electrolyte solute (i = # of ions)
Debye–Hückel theory
- Due to the ionic atmosphere surrounding an ion, the expected i value becomes non-ideal
ireal − 1
Degree of Dissociation (a) α=
iideal − 1
Acids and Bases

Definitions
1. Arrhenius Theory
- acid: yields H3O+ / H+ in solution (hydronium ion)
- base: yields OH- in solution
Example: Acid Base
−
HCl → H + Cl +
N aOH → N a + OH −
+
HCl + H2 O → H3 O+ + Cl− N H3 + H2 O → N H4+ + OH −

2. Brønsted-Lowry Theory
- acid: proton donor (proton: H+)
- base: proton acceptor
- includes conjugate acid-base pairs
- strong acids/bases produces a weak conjugate and vice versa
Example: Pairs:
HCl + H
+
Cl− HCl/Cl-
2 O → H3 O +

H acid base c.base c.acid 2
O/H3O+
CH3 COOH + H2 O → CH3 COO− + H3 O+

acid base c.base c.acid
−
H2 O + N H3 → OH
+ N H+
4
acid base c.base c.acid
Arrhenius bases ≠ Brønsted Lowry Bases

- metal hydroxides are only Arrhenius bases
3. Lewis Theory
- acid: electron pair acceptor
- base: electron pair donor
- forms a coordinate covalent bond
Example: H + + N H3 → N H4

acid base
Acidity: The ease of losing the H+ ion

Types of Acids
Binary Acids
- consists only of H and another atom
- acidity is dependent on electronegativity, bond strength and bond polarity
Examples: HF, HCl, HBr, HI, H2S
↑ bond polarity, ↑ bond strength, ↓ acidity
Example: Acidity: HF < HCl < HBr < HI (HF is already considered a weak acid)
Oxyacids
- consists of an ionizable H attached to an O
- oxygen-containing acids
Acidity in Difference of central atoms

↑ EN of central atom, ↑ Acidity
↓ size of central atom, ↑ Acidity
Example: HClO4 is more acidic than HBrO4
Acidity in Difference of the number of Oxygen Atoms

↑ O atoms, ↑ Acidity
Example: Acidity: HClO < HClO2 < HClO3 < HClO4
Examples of Strong Acids:
Polyproptic Acids
- ionizes through a series of steps
Example:
1st ionization : H2 SO4 + H2 O → H3 O+ + HSO4− (complete)
H2SO4 (diprotic):
2nd ionization : HSO4− + H2 O H3 O+ + SO42− (incomplete)
1st ionization : H3 P O4 + H2 O H3 O+ + H2 P O4− (incomplete)

H3PO4 (triprotic): 2nd ionization : H2 P O4− + H2 O H3 O+ + HP O42− (incomplete)
3rd ionization : HP O42− + H2 O H3 O+ + P O43− (incomplete)
- degree of ionization decreases after every ionization step
Titration and Neutralization

- volumetric process to determine the concentration of a sample
Acid-Base Titration:
analyte: acid titrant: base (solution of known concentration)
indicator: changes color at the endpoint
- for 1:1 mole ratio, use M1V1 = M2V2 ex. HCl + N aOH → N aCl + H2 O
- for other ratios, you can use normality or stoichiometry

Example: H2 SO4 + 2N aOH → N a2 SO4 + 2H2 O
analyte: 10.0 mL, H2SO4 titrant: 0.1M, 25.0 mL, NaOH

0.1 molb 0.025 Lb 1 mola 1
Ma = = 0.125Macid
1 Lb 1 2 molb 0.01 La
Chemical Thermodynamics
- measure of energy changes, spontaneity, etc.
Basic Concepts
System
- The part of the universe on which we wish to focus attention, or any part we want to
study.
Surroundings
- Everything outside the system.
Types of systems
1. Open Systems
- Has a boundary or wall that allows exchange of heat and matter with its surroundings.
- Also known as NONCONSERVATIVE system.
2. Closed Systems
- Has a boundary or wall that allows the exchange of heat but NOT matter with its
surroundings.
- The wall or boundary is known as the diathermal wall.
3. Isolated Systems
- Has a boundary or wall that does NOT allow the exchange of heat and matter with its
surroundings.
- The wall or boundary is known as the adiabatic wall.
Properties of a System
Extensive Properties
- They are dependent on the amount of matter, that is, the properties changes as the
quantity changes.
Examples: mass, moles, volume, etc.
Intensive Properties
- They are independent on the amount of matter.
Examples: density, molecular mass, boiling point, etc.
Extensive Property 1
Intensive Property =
Extensive Property 2
Examples: MM (g/mol), density (mass/vol)
State Functions
- The property of a system that depends only on its present state.
(dependent on initial/final states)
- They do not depend on the path taken or how the system arrived to its present state.
(path-independent)
Examples: ∆U, ∆H, ∆S, ∆G, ∆A, V, P, T
Non-state functions
- Path-dependent: The path should be taken into account when evaluating them.
- One needs to determine the change involved and not on the initial and final states.
Examples: Work and heat (w and q)
State functions can be related to one another using an equation of state.

Example: ideal gas equation PV = nRT
Non-state functions, can be only evaluated if we know the path or type of change.
Variables and Sign Conventions in Thermodynamics

ΔU = Change in Internal Energy q = Heat
ΔH = Change in Enthalpy w = Work
ΔS = Change in Entropy

ΔG = Change in Gibbs free energy
Unit of energy: Joule (J)

Other conversions: 1 calorie = 4.184 J
By convention, using the BANK system [(+) - deposit and (-) - withdrawal]
(+) q = heat is absorbed by the system (-) q = heat is released by the system
(+) w = work is done on the system (-) w = work is done by the system
(+) ΔH = the process is endothermic (-) ΔH = the process is exothermic
The First Law of Thermodynamics

- Law of Conservation of Energy
- The internal energy (U): the sum of the kinetic and potential energies of the system.
- The internal energy of the system can be changed by flow of work, heat or both
∆U = q + w
A common type of work associated with chemical processes is work done by a gas (through
expansion) or done to a gas (compression). For instance, in automobile engines, the heat
from combustion of fuels expands the gases in the cylinder to push back the piston. This
work translates into the motion of the car.
For gases, w = −P ∆V ΔV = change in volume upon expansion or compression.

Expansion: V2 > V1 Compression: V2 < V1
w = −P ∆V w = −P ∆V
= −P (V2 − V1 ) = −P (V2 − V1 )
= (−)(+) = (−)(−)
w = (−) w = (+)
Example: Calculate the work associated with the expansion of a gas from 46 L to 64 L at a
constant pressure of 15 atm.
1. Given: V1 = 46L ; V2 = 64L ; P = 15atm ; w =?

w = −P ∆V = −P (V2 − V1 )
= −(15)(64 − 46)
= −270Latm
Converting to Joules:

molK 0.314J
= −270Latm = −27357.75J = −27.36kJ
0.08206Latm molK
Latm J
Note: R = 0.08206 = 0.314 1Latm = 101.325J
molK molk
Example: A balloon is being inflated to its full extent by heating the air inside it. In the final
stages of this process, the volume of the balloon changes from 4.00 x 106 L to 4.50 x 106
L by the addition of 1.3 x 108 J as heat. Assuming that the gas expands against a constant
pressure of 1.0 atm. Calculate the ΔU for the process.

2. Given: V1 = 4.00 × 106 L ; V2 = 4.50 × 106 L ; P = 1.0atm ; q = 1.3 × 108 J
∆U = q + w = q − P ∆V = q − P (V2 − V1 )
= 1.3 × 108 J − (1.0atm)(4.50 × 106 L − 4.00 × 106 L)

J
= 1.3 × 108 J − (5.0 × 105 Latm)
101.325 Latm
= 1.79995 × 108 J
Applications of the First Law of Thermodynamics
at constant pressure: ∆H = q
The ∆H is commonly evaluated instead of the internal energy (ΔU).
1. Obtaining ∆H from ∆U
∆H = ∆U + ∆(P V )
Considering a chemical reaction, ∆Hrxn = ∆Urxn + ∆(P V )
P V = nRT
Assuming that all gaseous species are ideal gases: ∆(P V ) = ∆(nRT )
∆(P V ) = ∆ngas RT
∆ngas = moles of gaseous products – moles of gaseous reactants
Therefore,
∆Hrxn = ∆Urxn + ∆ngas RT
Also, for solids and liquids: ∆H ≈ ∆U
Heats of Reaction
Other Methods to Evaluate ΔH
1. Heat of Formation
- Heats of formation at standard state (25ºC and 1 atm), ΔHºf can be found in tables.
- The ΔHºf of pure elements at 25ºC and 1 atm are ZERO.
Examples: C(s, graphite), Br2(l), Hg(l), Cl2(g), Al(s)
For Gases: Standard state is at 1.00 atm * proper state must be indicated
For Solids: Standard state is at 1.00 M
Therefore,
∆Hrxn = Σ(n∆Hf◦ , products)–Σ(n∆Hf◦ , reactants)
Example: Calculate the ΔHrxn upon the combustion of 1 mole of glucose, C6H12O6.
Given: ΔHºf (CO2) = -393.5 kJ/mol
ΔHºf (H2O) = -285.6 kJ/mol
ΔHºf (glucose) = -1274 kJ/mol
C6 H12 O6 + 6O2 → 2CO2 + 6H2 O

−285.6kJ −393.5kJ −1274kJ 0kJ
= (6mol) + (6mol) – (1mol) + (6mol)
mol mol mol mol
= −2800.6kJ
Example: Methanol (CH3OH) is often used as a fuel in high performance engines in race
cars. Using the data above and below, calculate the enthalpy of combustion per gram of
methanol and compare that with the enthalpy of combustion per gram of octane (C8H18).
Given: ΔHºf (methanol) = -239 kJ/mol
ΔHºf (octane) = -269 kJ/mol
2CH3 OH + 3O2 → 2CO2 + 4H2 O

−285.6kJ −393.5kJ −239kJ 0kJ
= (4mol) + (2mol) – (2mol) + (3mol)
mol mol mol mol
= −1451.4kJ
2C8H18 + 25O2 → 16CO2 + 18H2 O

−285.6kJ −393.5kJ −269kJ 0kJ
= (18mol) + (16mol) – (2mol) + (25mol)
mol mol mol mol
= −10898.8kJ
2. Hess’ Law
- Since enthalpy is a state function it follows that in going from a particular set of reactants
to a particular set of products, the change in enthalpy is the same whether the reaction
takes place in one step or in a series of steps.
- Evaluation of ∆H when ∆Hºf data is not available
- The ΔH of such reactions can be evaluated using several steps but with the net reaction
equal to the desired reaction.
DESIRED RXN: N2 (g) + 2O2 (g) ⇒ 2NO2 (g) ΔH1 = 68 kJ

N2 (g) + O2 (g) ⇒ 2NO (g) ΔH2 = 180 kJ
2NO (g) + O2 (g) ⇒ 2NO2 (g) ΔH3 = -112 kJ
NET: N2 (g) + 2O2 (g) ⇒ 2NO2 (g) ΔH2 + ΔH3 = 68 kJ
Note:
1. If the reaction is reversed, the sign of ΔH is also reversed.
2. The magnitude of ΔH is directly proportional to the quantities of reactants and products in
the reaction. If the coefficients in a balanced reaction are multiplied by an integer, the value
of ΔH is multiplied by the same integer.
Example: Diborane (B2H6) is a highly reactive boron hydride, which was once considered as
a possible rocket fuel for the U.S space program. Calculate ΔH for the synthesis of diborane
from its elements.
2B(s) + 3H2(g) → B2 H6(g)
Using the following data:
Reaction ΔH
2B (s) + 3/2O2 (g) ⇒ B2O3 (s) -1273 kJ
B2H6 (g) + 3O2 (g) ⇒ B2O3 (s) + 3H2O (g) -2035 kJ
H2 (g) + 1/2O2 (g) ⇒ H2O (l) -286 kJ
H2O (l) ⇒ H2O (g) 44 kJ

3. Evaluation of Lattice Enthalpy, ΔHlattice (Born-Haber Cycle)
- the energy needed to separate an ionic lattice into gaseous ions or the energy released
when component ions form ionic compounds. Since, this cannot be determined exactly by
experiment, but can be envisioned as the formation of an ionic compound occurring in a
series of steps.
Reaction ΔH
Li (s) ⇒ Li (g) ∆Hsub = 161 kJ
Li (g) ⇒ Li+ (g) + e 1st Ionization Energy = 520 kJ
1/2F2 (g) ⇒ F (g) ∆Hdiss = 77 kJ
F (g) + e ⇒ F- (g) Electron Affinity = -328 kJ
Li (s) + 1/2F2 (g) ⇒ LiF (s) ∆Hºf = -617 kJ
What is the lattice enthalpy of LiF?
4. ΔHºf from Bond Enthalpies
Example: H2(g) + F2(g) → 2HF(g)
∆Hrxn = Σ(n∆H, bonds f ormed)–Σ(n∆H, bonds broken)
Therefore, ∆H = BEH−H + BEF −F –2BEH−F
Calculate the ΔHof of HF. Given that BE of H-H is 432 kJ, F-F is 154 kJ and H-F is 565 kJ.
The Second Law of Thermodynamics

- basis for predicting if a reaction will be spontaneous or non-spontaneous.
- spontaneous if a process will cause an increase in entropy of the universe
- The entropy of the universe is increasing.
Spontaneous - occurs without outside intervention

- it occurs and liberates energy at the same time
Non-spontaneous - requires energy to carry out
Measure of spontaneity: S or entropy.
Entropy
- Degree of disorder/randomness in a system
- difficult to measure and quantify
- not all reactions with ↑∆S are spontaneous
Gibb’s Free Energy (ΔG)

- expendable energy of the system
- better measure because it takes into account ∆H and ∆S
At constant pressure:
∆G = ∆H − T ∆S (The AGAHTAS equation)
Therefore, ΔG < 0: (-) Spontaneous Process at any T

ΔG > 0: (+) Non-spontaneous Process at any T
ΔG = 0: System at Equilibrium
Cases Common in Chemical Reactions

∆H T ∆S = ∆G
- any + -
+ any - +
Cases Common in Physical Changes

∆H T ∆S = ∆G
- low - -
- high - +
+ high + -
+ low + +

In physical transformations:
qrev ∆Htransition
∆S = ∆S =
Trev Ttransition
Example: Melting: ∆Hfusion = qrev Tmelt = Trev
Where, qr is the heat released or absorbed while T is temperature in Kelvin.
Let us see why water freezes spontaneously at -10ºC while not at 10ºC.
Given:
ΔHº = 6.03 x 103 J/mol ΔSº = (6.03 x 103 J/mol)/273 K
Ttransition = 273 K ΔSº = 22.1 J/mol K
T (ºC) T (K) ΔHº (J/mol) ΔSº (J/mol K) TΔS (J/mol) ΔGº (J/mol)
-10 263 6.03 x 103 22.1 5.81 x 103 2.2 x 102
0 273 6.03 x 103 22.1 6.03 x 103 0
10 283 6.03 x 103 22.1 6.25 x 103 -2.2 x102
Note: Both ΔS and ΔG are STATE FUNCTIONS!
Therefore,
∆S = Σ(n∆S, products)–Σ(n∆S, reactants)
∆G = Σ(n∆G, products)–Σ(n∆G, reactants)
Example: Consider the reaction 2SO2 (g) + O2 (g) ⇒ 2SO3 (g)

The reaction was carried out at 25ºC and 1 atm.
Calculate the ΔH, ΔS and ΔG using the following data:
Substance ΔHf (kJ/mol) ΔS (J/mol K)

SO2 (g) -297 248
SO3 (g) -396 257
O2 (g) 0 205
Is the process spontaneous or non-spontaneous?
Example:
1. Given: ∆Hf = 1440 cal/mol ; Tf = 0◦ C

a) at − 5◦ C
∆G = ∆H − T ∆S
∆Hf 1440 cal/mol
= ∆H − T ∆S =
Tf 273K
1440 cal/mol = 5.27 cal/molK
= 1440 cal/mol − 268K
273K = 5.27 eu
= 27.64 cal/mol
b) at 0◦ C c) at 5◦ C
∆G = ∆H − T ∆S ∆G = ∆H − T ∆S
5.27cal 5.27cal
= 1440 cal/mol − 273K = 1440 cal/mol − 278K
molK molK
=0 = −25.06 cal/mol
Using Standard Entropy of Formation (Sfº)

Example: Given the data below:
6CO2 + 6H2 O → C6 H12 O6 + 6O2
ΔH = 2806 kJ/mol
ΔS (CO2 ) = 214 J/mol K ΔS (glucose) = 212 J/mol K
ΔS (H2O) = 70 J/mol K ΔS (O2) = 205 J/mol K
Is photosynthesis a spontaneous at 25ºC?
∆G = ∆H − T ∆S
= ∆H − T [Σ(n∆S, products)–Σ(n∆S, reactants)]

212J 205J 214J 70J
= ∆H − T (1mol) + (6mol) – (6mol) + (6mol)
molK molK molK molK

−262J
= 2806kJ − 298K
K

−0.262kJ
= 2806kJ − 298K
K
= 2884.08kJ (not spontaneous at 25o C)
Third Law of Thermodynamics

- At absolute zero, or 0 K, -273oC, the entropy of a pure crystalline solid is zero.
S0K = 0
*With this, we are able to evaluate the absolute values of entropy. That is, if we start heating
a pure crystalline solid, from T = 0 K to T we get:
∆S = Sf − Si
∆S = Sf − S0K
∆S = Sf
(No delta (∆S) when reported)
Chemical Kinetics
- area concerned with the speed or rates of reaction
- how fast or slow a reaction occurs
Rate
- measured change of concentration of reactants/products per unit time
- you can use any reactant/product to state rate
Example: A ⇒ B
−∆[A]
reactant: rate = (rate of disappearance of A)
∆t
∆[B]
product: rate = (rate of appearance of B)
∆t
The Rate of Reaction:
A decreases with time
B increases with time
Also dependent on Stoichiometry

1 ∆[A] ∆[B]
Example: 2A ⇒ B reactant: rate = − product: rate =
2 ∆t ∆t
aA + bB → cC + dD
1 ∆[A] 1 ∆[C]
Reactant A: rate = − Product C: rate =
a ∆t c ∆t
1 ∆[B] 1 ∆[D]
Reactant B: rate = − Product D: rate =
b ∆t d ∆t
Theories on Reaction Rates
Collision Theory
- rate is proportional to (number of collisions)/(time) [frequency of collision]
- ↑frequency, ↑rate
- effective collision is needed
Effective Collision
1. colliding molecules: energy ≥ minimum energy requirement
(activation energy (Ea) or energy barrier)
activation energy: the minimum amount of energy required to initiate a chemical reaction
2. proper orientation is needed
Reaction Profile
- plot of the potential energy vs. time of a reaction (progress)
Conclusions from Reaction Profiles:

- the one with a lower Ea will occur faster ↓Ea: faster ↑Ea: slower
- you can determine the energy of the reactants and products
- you can determine if the reaction is exothermic/endothermic
- if the reaction is reversible, you can compute for the Ea of both directions
- you can also determine the number of steps in the reaction
- single step: concerted
- no. of peaks = no. of steps
Proper Orientations
- if the molecules are not properly oriented, they will not form the products
Transition State Theory

- the reactants will form a transition site before forming the products
- unstable arrangement of atoms
- reactants in a short-lived, high-energy, intermediate state
Initial: A + B-B Transition: A--B--B Final: A-B + B
- exact structure cannot be determined

- the rate of the reaction is dependent on the energy required to form the transition state
↓energy requirement: faster ↑energy requirement: slower
- peaks in reaction profile: transition state
- multistep reactions have many transition states
Factors Affecting Rates of Reactions

1. Nature of Reactants
- some reactions are inherently fast/slow
- dependent on the Ea of the reaction
- liquid vs. gas (different phases)
- Ea
- position in the reactivity series
2. Surface Area
- ↑SA, ↑ rate
- due to the high number of molecules exposed to collision
3. Temperature
- ↑T, ↑KE, ↑mobility, ↑frequency of collision, ↑rate
- not dependent if the reaction is exothermic/endothermic
- Arrhenius Equation - relates rate with temperature
- k: specific rate constant

4. Concentration of Reactants
- Law of Mass Action ↑conc'n, ↑no. of molecules
- ↑conc'n, ↑frequency of collision, ↑rate
- exception: Zero Order (concentration does not affect rate)
Rate Law Expression

k = specific rate constant
x y z
rate = k[A] [B] [C] [A] = molar concentration
x/y/z = orders of reaction
order of reaction - magnitude of effect of change in concentration

zero order: [A]0 = 1
Determination of Order
- always experimentally determined and not always = coefficient in balanced equation
Method of Initial Rates

- given a set of experimental data comparing different rates of reaction
- choose one reactant to vary with the other
reactants
x being constant
rateA [A]A
- get the general ratio: =
rateB [A]B
- solve for x to get the order
- overall order = ∑(n orders)
- with all orders determined, you can find the value of k.
5. Presence of Catalyst
- a substance that increases the rate of the reaction without itself being consumed
Types of Catalysis:
1. Homogenous - reactants and catalysts are dispersed in the same phase
intermediate: valleys in the reaction profile
2. Heterogenous - reactants and catalysts are not of the same phase

Example: catalytic hydrogenation
- the only factor that affects activation energy

- catalysts lower the activation energy
- catalysts change the reaction into a multi-step reaction with lower Ea
Chemical Equilibrium
Molecular Equilibrium
Definitions
Kinetic Definition: rate of forward reaction = rate of backward reaction
In a reversible reaction: aA(g) + bB(g) cC(g) + dD(g)
a b c d
Rate Laws: Kf [A] [B] = Kb [C] [D] In equilibrium, we assume order is
equal to coefficient
Kf [C]c [D]d PC c PD d
Then, Keq = KC = = KP =
Kb [A]a [B]b P A a PB b
Thermodynamic Definition: ∆G = 0
∆G = ∆G◦ + RT lnQ Q = reaction quotient

at equilibrium:
0 = ∆G◦ + RT lnKeq
[C]c [D]d
Q= −∆G◦
[A]a [B]b lnKeq =
RT
−∆G◦
Keq = e RT
Types of Equilibrium:
1. Homogenous Equilibrium - reactants and products are of the same phase
[H2 ][I2 ]
Example: 2HI(g) H2(g) + I2(g) KC =
[HI]2
2. Heterogenous Equilibrium - reacyants and products are present in different phases
Example: CaCO3(g) CaO(s) + CO2(g) KC = [CO2 ] ; KP = PCO2
KC does not include concentration terms of pure solids/liquids
AgCl(s) Ag + (aq) + Cl− (aq) KSP = [Ag + ][Cl− ] KSP = solubility product constant
KSP is for partially soluble salts
[H3 O+ ][CH3 COO− ]

CH3 COOH + H2 O H3 O+ + CH3 COO− Ka =
[CH3 COOH]
- any mixture with acetic acid is always in equilibrium
- Ka = acid dissociation constant Kb = base dissociation constant
Factors Affecting Equilibrium

Le Chatelier's Principle
- when a stress factor is applied to a system in equilibrium, the system will shift to relieve the
stress (relieve the balance)
factors: changes in concentration, P, V, T, addition of catalyst
2A(g) + B(g) P(g) + heat
Stresses:
Addition of A: shift to the RIGHT Removal of A: shift to the LEFT
Addition of B: shift to the RIGHT Removal of B: shift to the LEFT
Addition of P: shift to the LEFT Removal of P: shift to the RIGHT
↑P (resulting in ↓V) shift to the RIGHT ↓P (resulting in ↑V) shift to the LEFT
↑P, shift to the lesser number of moles) ↓P, (shift to the higher number of moles)
↑T: shift to the LEFT ↓T shift to the RIGHT

↑T favors endothermic processes ↓T favors exothermic processes
catalyst: no shift in equilibrium, they affect both the forward and backward reactions
Example:
S F eCN
−
F e3+ + CN

2+
S
orange colorless blood red
Stresses:
Addition of Fe(NO3)3: darker (↑[Fe3+])
Addition of KSCN: darker (↑[CNS-])
Addition of AgNO3: Ag+ + SCN- ⇒ AgSCN (white precipitate) LEFT (↓[CNS-])
Addition of NaF: lighter (forms FeF63-) (↓[Fe3+])
Addition of KCl: lighter (forms FeCl63- (↓[Fe3+]) or by dilution)
or no shift: KCl does not react with the species
CH3 COOH + H2 O H3 O+ + CH3 COO−

Stresses:
Addition of NaCH3COO: NaCH3COO ⇒ Na+ + CH3COO- LEFT
(common-ion effect: presence of a common ion suppresses the ionization of an electrolyte)
Addition of HCl: HCl ⇒ H+ + Cl- LEFT (common-ion effect)
Addition of NaOH: NaOH ⇒ Na+ + OH- (neutralizes H3O+) RIGHT
Addition of NaCl: no shift
CaCO3(g) CaO(s) + CO2(g)
Stresses:
Addition of CO2: LEFT
Addition of CaO: no shift (solid, is not involved in Keq)
Addition of Inert Gas (constant V): ↑PTOTAL
Finding KC from equilibrium concentrations
1. Given: CO(g) + Cl2(g) COCl2(g)

Equilibrium Concentrations: CO : 1.2 × 10−4 M Cl2 : 0.054M COCl2 : 0.14M
[COCl2 ] (0.14M )
KC = = = 216.05
[CO][Cl2 ] (1.2 × 10−4 M )(0.054M )
2. Given: H2(g) + I2(g) 2HI(g)

Initial Concentrations: H2 : 1 × 10−3 M I2 : 2 × 10−3 M
Equilibrium Concentrations: HI : 1.87 × 10−3 M
ICE table
H2 I2 HI
I 1 × 10−3 M 2 × 10−3 M 0M
C* -x M -x M +2x M
E 1 × 10−3 − x M 2 × 10−3 − x M 2x M
*C-row follows stoichiometric coefficient
[HI] = 1.87 × 10−3 M = 2x x = 9.35 × 10−4 M

[H2 ] = 1 × 10−3 − 9.35 × 10−4 M = 6.5 × 10−5 M
[I2 ] = 2 × 10−3 − 9.35 × 10−4 M = 1.065 × 10−3 M
[HI]2 (1.87 × 10−3 M )2

KC = = = 50.51
[H2 ][I2 ] (6.5 × 10−5 M )(1.065 × 10−3 M )
Finding equilibrium concentrations from KC
3. Given: H2(g) + I2(g) 2HI(g) [HI]2

KC =
Initial Concentrations: H2 : 1mol I2 : 2mol in 1.0L [H2 ][I2 ]
KC = 50.5 (2x)2
50.5 =
(1 − x)(2 − x)
H2 I2 HI 46.5x2 − 151.5x + 101 = 0
I 1M 2M 0M x = 2.92 x = 0.93
C -x M -x M +2x M
E 1-x M 2-x M 2x M
[HI] = 2 × 0.93 = 1.86M
[H2 ] = 1 − 0.93M = 0.07M
[I2 ] = 2 − 0.93M = 1.07M

4. Given: COCl2(g) CO(g) + Cl2(g)
Initial Concentrations: COCl2 : 3.50 × 10−3 M CO : 1.11 × 10−5 M Cl2 : 3.25 × 10−6 M
KC = 1.19 × 10−10
Is the system in equilibrium?
[CO][Cl2 ] (1.11 × 10−5 M )(3.25 × 10−6 M )
QC = = = 1.19 × 10−8
[COCl2 ] (3.50 × 10−3 M )
Note:
If KC > QC , there are more reactants than in equilibrium (forward shift)
If KC = QC , there is equilibrium
If KC < QC , there are more products than in equilibrium (backward shift)
KC < QC , therefore, there is no equilibrium
COCl2(g) CO(g) Cl2(g)

I 3.50 × 10−3 M 1.11 × 10−5 M 3.25 × 10−6 M
C +x M -x M -x M
E 3.50 × 10−3 + x M 1.11 × 10−5 − x M 3.25 × 10−6 − x M
[CO][Cl2 ]
KC =
[COCl2 ]
(1.11 × 10−5 M )(3.25 × 10−6 M )
1.19 × 10−10 =
(3.50 × 10−3 M )
x = 1.12 × 10−5 x = 3.15 × 10−6
[COCl2 ] = 3.50 × 10−3 M

[CO] = 7.95 × 10−6 M
[Cl2 ] = 1.00 × 10−7 M
Ionic Equilibrium
- between weak acids and weak bases
- any solution of a weak acid or a weak base is in equilibrium
Example 1:
[H3 O+ ][CH3 COO− ]
Ka =
CH3 COOH + H2 O H3 O + CH3 COO
+ −
[CH3 COOH]
Ka = acid dissociation constant
Ka for CH3COOH = 1.8x10-5

- it is a small value, which means that the concentration of the products is much less
than the concentration of the reactants
Example 2:
[N H3 OH][OH − ]
Kb =
N H3 + H2 O N H4 + + OH − [N H3 ]
Kb = base dissociation constant
Kb for NH3 = 1.8x10-5
Ka from % ionization
1. Given: HA + H2 O H3 O+ + A−
0.010 M HA; 2.0% ionization
HA H3 O+ A−
48 | I 0.01 M 0M Chemistry
0 14:
M Fundamentals of General Chemistry I
C -(0.02×0.01) M +(0.02×0.01) M +(0.02×0.01) M
1. Given: HA + H2 O H3 O + A
0.010 M HA; 2.0% ionization
HA H3 O+ A−
I 0.01 M 0M 0M
C -(0.02×0.01) M +(0.02×0.01) M +(0.02×0.01) M
E 9.8 × 10−3 M 2 × 10−4 M 2 × 10−4 M
[H3 O+ ][A− ] (2 × 10−4 M )(2 × 10−4 M )

Ka = = = 4.08 × 10−6
[HA] (9.8 × 10−3 M )
% ionization from Ka
2. Given: CH3 COOH + H2 O H3 O+ + CH3 COO−

0.010 M CH3 COOH; Ka = 1.8 × 10−5
CH3 COOH H3 O+ CH3 COO−

I 0.01 M 0M 0M
C -x M +x M +x M
E 0.01-x M xM xM
[H3 O+ ][CH3 COO− ]

Ka =
[CH3 COOH]
(x)(x)
1.8 × 10−5 =
0.01 − x
C
Rounding off: If ≥ 100, then you can round off
Keq
Therefore:
x2
1.8 × 10−5 =
0.01
x = (1.8 × 10−5 )(0.01)
= 4.24 × 10−4 = [H3 O+ ]
ionized f orm 4.24 × 10−4

%ionization = × 100 = × 100 = 4.24%
unionized f orm 0.01
Note: kay sir Quiming lang yata pwede yung round-off thing
pH = −log[H3 O+ ] pOH = −log[OH − ]
autoionization of H2 O: H2 O + H2 O H3 O+ + OH−
at 25◦ C, [H3 O+ ] = [OH − ] = 1.0 × 10−7 M
KW = equilibrium constant for H2 O

= [H3 O+ ][OH − ] −logKW = −log[H3 O+ ] + −log[OH − ]
= (1.0 × 10−7 M )(1.0 × 10−7 M ) 14 = pH + pOH
= 1.0 × 10−14
1. pH of strong acids and bases: HCl → H+ + Cl− full ionization
Given: 0.1 M of HCl

pH = −log[0.1M ] = 1

2. pH of weak acids and bases

Given: HCN + H2 O H3 O+ + CN −
0.2 M HCN; Ka = 4.9 × 10−10
HCN H3 O + CN−
I 0.2 M 0M 0M
C -x M +x M +x M
E 0.2-x M xM xM
[H3 O+ ][CN − ]
Ka =
[HCN ]
(x)(x)
4.9 × 10−10 =
0.2 − x
0.2
≥ 100, therefore you can round off
4.9 × 10−10
x2
4.9 × 10−10 =
0.2
x = (4.9 × 10−10 )(0.2)
= 9.90 × 10−6 = [H3 O+ ]
pH = −log[H3 O+ ]
= −log(9.90 × 10−6 M )
= 5.00

Note: if roundable: pH = -log Ka × C
3. Salts: formed by an acid plus a base

a. Strong Acid + Strong Base = Neutral Salt
Example: HCl + N aOH → N aCl + H2 O
Na+ is a metal
Cl- is a very weak base (conjugate of a very strong acid)
b. Weak Acid + Strong Base = Basic Salt

Example: CH3 COOH + N aOH → N aCH3 COO + H2 O
Na+ is a metal
CH3COO- : CH3 COO− + H2 O CH3 COOH + OH −
c. Strong Acid + Weak Base = Acidic Salt

Example: HCl + N H4 OH → N H4 Cl + H2 O
NH4+ : N H4 + + H2 O N H3 + H3 O+
Cl- is a very weak base (conjugate of a very strong acid)
d. Weak Acid + Weak Base = Acidic/Basic/Neutral

- it is dependent on the Ka of the acid and the Kb of the salt
Ka = Kb, Neutral Salt
CH3 COOH + N H4 OH → N H4 CH3 COO + H2 O
Example:
Ka of CH3 COOH = Kb of N H4 OH
Ka > Kb, Acidic Salt
Ka < Kb, Basic Salt

Chemistry 14: The Fundamentals of General Chemistry I

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Chemistry 14: The Fundamentals of General Chemistry I

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CHEMISTRY 14

The Fundamentals of General Chemistry I

2nd Semester || AY 2010-2011 || Section TFC

ii | Chemistry 14: Fundamentals of General Chemistry I

The Development of the Different Atomic Models

John Dalton - Billiard Ball Model

J.J. Thompson - Plum Pudding/Raisin Bread Model

Ernest Rutherford - Nuclear Model

Modern Model (Rutherford) vs. Dalton

Noel S. Quiming Notes by A-Log | 1

Atomic Mass Unit (amu)

Atomic No. (Z) = No. of protons

Mass No. (A) = No. of protons + No. of neutrons

For Cations (+): No. of protons > No. of electrons

No. of protons No. of electrons No. of neutrons

Examples: 1H 2H 3H; 12C 13C 14C; 235U 238U

No. of protons No. of neutrons Mass Number

C - used in NMR (Nuclear Magnetic Resonance)

C - used in carbon dating t½ = 5700 years

2 | Chemistry 14: Fundamentals of General Chemistry I

Niels Bohr - Planetary Model

hc h = P lanck  s constant c = Speed of Light

Quantum Mechanical Model and Quantum Numbers

Noel S. Quiming Notes by A-Log | 3

Pauli’s Exclusion Principle

No. of orbitals No. of electrons

4 | Chemistry 14: Fundamentals of General Chemistry I

Hund's Rule of maximum Multiplicity

Atoms at ground state can undergo excitation into an excited state:

Quantum Numbers for electrons in an orbital:

1s: ↓↑ (1, 0, 0, -½), (1, 0, 0, +½)

Differentiating Electron: last entering electron

paramagnetic - if an atom has an unpaired electron

Shortcut: Using noble gases

Valence electrons - electrons occupying the outermost energy level

Ta: 1s22s22p63s23p64s23d104p65s24d105p66s24p145d3 = [Xe]6s24p145d3

Sr: 1s22s22p63s23p64s23d104p65s2= [Kr]5s2

Given: Differentiating Elctron: (4, 1, 0, +½)

Stability: Ar > P > S

The Periodic Table

Dalton's Chemical Symbols

Dobereiner's Law of Triads

Newland's Law of Octaves

Mendeleev and Meyer's Periodic Law

Moseley's Periodic Law

- noble gases have high IP because of stability

Effective Nuclear Charge

The Chemical Bond

Ionic or Electrovalent Bond

8 | Chemistry 14: Fundamentals of General Chemistry I

The Covalent Bond

Normal Covalency No.

Coordinate Covalent Bond

Formal Charge = Group No. - (No. of unshared electrons + No. of bonds)

Lewis Dot Structure

Noel S. Quiming Notes by A-Log | 9

Central atom: highest covalency number

Contributing Structures based on Formal Charges

Resonance Structures - different lewis structures for the same compound

Structure 1: Double bond to O1

- the third structure is not contributing because

Structure 1: Double bond to both S and N

hc h = P lanck s constant c = Speed of Light