1

Gen Chem Day 1-Atomic and Nuclear Structure

Atomic Stucture
Bohr model oI the atom
s, p, d, I orbitals
nucleus (protons and neutrons)
electron cloud
atomic # Z (# oI protons)
mass # NZ (N # oI neutrons)
isotopes
atomic weight

Periodic Table
Organization
Metals vs. non-metals
groups and periods
Alkali metals, alkaline earth metals, noble gases, halogens, transition metals

Electron ConIigurations
Standard and Noble Gas conIigurations
Exceptions (Cr, Mo and Cu, Ag, Au)
Ions (transition metals too)
# valence electrons
Paramagnetic vs. diamagnetic

Quantum Numbers
# Name What? Range
n principal Shell |1.|
l azimuthal Subshell (type oI orbital) |0.(n-1)|
m
l
magnetic SpeciIic orbital (orientation in space) |-l.l|
m
s
spin Up or down 1/2 or -1/2

Electron Energy Levels
Ground state vs. excited state
Emission vs. absorption spectra

2
Nuclear Chemistry
Nuclear Structure and the strong nuclear Iorce
Nuclear symbols
Symbols Ior o, p, n, |, and (penetrating power)

Unstable nuclei are radioactive
1) Even numbers oI protons and/or neutrons are stable
2) N/Z ratio ~1 are more stable (Ior Z20)---belt oI stability
3) Magic numbers are more stable (2, 8, 20, 50, 82, 126)

Nuclear Rxns
Parent daughter(s) energy mass is always lost (Emc
2
)

Routes of Decay What? Who?
1) o-decay Reduces Mass # Large nuclei (Z~83) below the belt
2) |
-
decay (| emission) np N/Z is too high
2) |

decay (Positron emission) pn N/Z is too low

3) Electron Capture pn N/Z is too low
3) -decay

Rate oI Decay
Always 1
st
order (lnN lnN
0
kt)
HalI-liIe (Iractions, percents, masses, activities)

Nuclear Binding Energy (total vs. per nucleon)
mass deIect (Am)

E Amc
2
Am must be in kg 6.02 x 10
23
a.m.u. 1g

56
Fe has the highest nuclear binding energy per nucleon
Gen Chem Day 2-Periodic Trends and Bonding

Periodic Trends
Atomic Radius

3
Ionic Radius
Isoelectronic Series

1
st
Ionization Energy
The energy required to remove an electron


2
nd
, 3
rd
, 4
th
, etc.




Electron AIIinity
Energy change associated with gaining an electron
F
He
F
Cl
Br
I
Fr





Electronegativity





Bonding
Covalent (molecular or network solids) non-metal with non-metal

Ionic (ionic crystals) metal with non-metal

Metallic (metallic lattices) metal with metal


Physical Properties
Ionic compounds high m.p. and b.p., brittle

Metallic high m.p. and b.p. (usually), conduct electricity, malleable, ductile

Molecular lower m.p. and b.p.


Molecular Structures
Lewis Dot Symbols (Ex. CH
4
, CO
2
, SF
4
)
Formal Charges
Polar Covalent Bonds
Coordinate Covalent Bonds
4
Molecular Geometry
VSEPR Theory

Hybridization

Electron
Domains
Hybridization Bond Angle Electron Domain
Geometry
Non-bonding
Pairs e
-

Molecular Geometry
2 sp 180 Linear 0 Linear
3 sp
2
120 Trigonal planar 0 Trigonal planar
1 Bent
4 sp
3
109.5 Tetrahedral 0 Tetrahedral
1 Trigonal pyramidal
2 Bent
5 sp
3
d 90, 120 Trigonal bipyramidal 0 Trigonal bipyramidal
1 See-saw
2 T-shaped
3 linear
6 sp
3
d
2
90 Octahedral 0 Octahedral
1 Square pyramidal
2 Square planar






Intermolecular Forces
Hydrogen Bonding
F-H, O-H, or N-H bond required in a pure substance
F, O, or N to hydrogen bond with H
2
O

Dipole-dipole (and ion-dipole, dipole-induced dipole)
Intermolecular Iorce Ior polar molecules

London Dispersion Forces (Van der Waals)
A temporary or transient dipole. All molecules have these and the more surIace area, the greater the London
dispersion Iorces.

Higher Intermolecular Forces lead to higher boiling pts, higher melting pts, higher viscosity, higher surIace
tension, but lower vapor pressure


Gen Chem Day 3-Phases and Gases

Phases
Physical Changes
Phase Transitions
Endo- vs. Exothermic
Entropy Changes

solid liquid gas
crystallization condensation
deposition
solid liquid gas
Iusion vaporization
sublimation
AH ~ 0
(Endothermic)
AS ~ 0
AH 0
(Exothermic)
AS 0

Calorimetry (q mcAT)
Diagram









Phase Diagrams
General H
2
O CO
2













5
Gases
Kinetic Molecular Theory
Ideal Gas Assumptions
1) Gas molecules themselves have no volume
2) No intermolecular attractions between molecules (all collisions are elastic)
Kinetic energy T

Characteristics oI Gases
Volume (Liters; 1cm
3
1mL)

Temperature (C or K)

Pressure (1atm 760 torr 760mmHg)

STP (0C and 1atm) 1 mole gas 22.4L STP

Ideal Gas Law
PV nRT (Works best at low P, high T, and Ior non-polar gases)

Boyle`s Law P
V
1


Charle`s Law V T

Avogadro`s Law V n

Combined gas law
2 2
2 2
1 1
1 1
T n
V P
T n
V P
=


Dalton`s Law oI Partial Pressures P
Tot
P
A
P
B
. P
A
_
A
P
Tot


Graham`s Law oI EIIusion
1
2
2
1
M
M
r
r
=



Stoichiometry
Mole to mole ratios
Molar Mass
Avogadro`s number 6.02x10
23

1 mole gas 22.4L STP
6
Gen Chem Day 4-Solutions and Kinetics
Solutions
Vocab.
Solvent, solute, saturated, unsaturated, supersaturated

Concentration
ln Lso
molsolute
Molarity =
kgsolvent
molsolute
Molality =
moles total
molsolute
ion moleIract =

Solubility Rules
1) All Group I metal, NH
4

, NO
3
-
ClO
4
-
, and C
2
H
3
O
2
-
(acetate) salts are soluble.
2) Most Ag

, Pb
2
, and Hg
2
2
salts are insoluble.

Phase Solubility in Liquids Rules
1) Solids are more soluble at higher temperatures
2) Gases are less soluble at higher temperatures
3) Gases are more soluble at higher pressures

Colligative Properties
van`t HoII Iactor
1) Freezing Pt. Depression m iK T
F F
= A







2) Boiling Pt. Elevation m iK T
B B
= A







3) Vapor Pressure Depression (Raoult`s Law)
Total A A
P P _ =







4) Osmotic Pressure t iMRT

7
Kinetics
Kinetics vs. Thermodynamics

Rate expressions
2H
2
O
(g)
2H
2(g)
O
2(g)
t
O H
A
A
2
| |
2

t
H
A
A
2
| |
2

t
O
A
A | |
2


Rxn Coordinate Diagram IdentiIy AH, E
a
, transition state (activated complex), intermediates


Rate Determining Step (slow step)

Catalyst speeds up a reaction by lowering the activation energy by providing an alternate mechanism
(pathway) Ior the reaction to occur

Rate laws
rate k|A|
x
|B|
y

For the reaction 2NO
(g)
Cl
2(g)
2NOCl
(g)
, the Iollowing results were obtained:

|NO|
0
(mol/L) |Cl
2
|
0
(mol/L) Initial Rate (mol/L
.
s)
0.10 0.10 0.18
0.10 0.20 0.36
0.20 0.20 1.44
What is the rate law Ior this reaction?


What is the overall rxn order?

What is the rate constant?

Mechanisms

O
3
O
2
O (rapid equilibrium) or (Iast)
O O
3
2O
2
(slow)

What is the intermediate?

What is the rate law?
8
Gen Chem Day 5-Equilibrium and Acid/Base
Equilibrium
DeIinition oI Equilibrium Iorward rate reverse rate

Equilibrium constant (mass action ratio)






K
eq
Meaning
K ~~ 1 Products Iavored at eq.
K 1 Reactants Iavored at eq.
K ~ 1 Considerable Prod/React
present at eq.
Reaction Quotient
Q Result
QK shiIt right
Q~K shiIt leIt
QK at equilibrium

Le Chatelier`s Principle
2C
(s)
O
2(s)
2CO
(g)





Solubility
K
sp

Common Ion EIIect

Solubility
What is the molar solubility oI AgCl (K
sp
1.8x10
-10
)?




The molar solubility oI BiI
3
is 1.32x10
-5
. Calculate K
sp
.




Common Ion EIIect
What is the molar solubility oI AgCl in 0.1M HCl? (K
sp
1.8x10
-10
)




Precipitation
To a 0.0001M solution oI Mg(NO
3
)
2
, NaOH was added to a Iinal
concentration oI 0.001M. Did a precipitate Iorm? (K
sp
Mg(OH)
2
1.6x10
-12
)

9
Acids and Bases
Acid Base
Arrhenious H

donor in H
2
O OH
-
donor in H
2
O
Bronsted-Lowry H

donor H

acceptor
Lewis Electron acceptor Electron donor

Conjugate Acid / Base Pairs (Amphoteric substances)


Strong acids HClO
4
, H
2
SO
4
, HI, HBr, HCl, HNO
3
, HClO
3

Strong bases - Group 1 metal hydroxides, Ba(OH)
2
, Sr(OH)
2
, Ca(OH)
2



Binary acid trend
Binary acid trend




Oxoacid trends
1) More oxygens, more acidic
2) More electronegative heteroatom, more acidic



pH scale
pH, pOH, |H

|, |OH
-
|; iI
you know 1 oI the 4, you
can calculate the other 3.








pH oI strong acids


10
pH oI weak acids
Acid dissociation in water: HA H
2
O H
3
O

A
-

| || |
| | HA
A O H
K
a
+
=
3

| )| ( | | HA Ka H =
+



pH oI weak bases
Base dissociation in water: A
-
H
2
O HA OH
-

| || |
| |

=
A
HA OH
K
b

| )| ( | |

= A Kb OH



K
a
K
b
K
w



Neutralization rxns


Neutral
Anions
Cl
-

Br
-

I
-

NO
3
-

ClO
4
-

ClO
3
-


Acidic
Anion
HSO
4
-


Almost all
other
anions are
bases.
Neutral
Cations
Li

Na

Rb

Cs

Ca
2

Sr
2

Ba
2


All other
cations are
acidic;
the more
positively
charged, the
more acidic.




Hydrolysis oI salts







BuIIers
11
| |
| |
log
HA
A
pK pH
a

+ =







Titrations
pH at Equivalence Pt.
Strong Acid / Strong Base 7
Weak Acid / Strong Base ~7
Strong Acid / Weak Base 7
n
A
M
A
V
A
n
A
M
B
V
B



Gen Chem Day 6-Thermodynamics
Three laws oI thermodynamics
1) Conservation oI energy (Energy can`t be created or destroyed).
2) For a spontaneous process, the entropy oI the universe increases.
3) A perIect crystal at 0K has zero entropy.

AE q w w -PAV

Gas in a piston
1) TransIer oI heat (lock piston)
2) Expanding gases cool; compressing gases warm
3) Isobaric (AP 0)
4) Isochoric (AV 0 so w 0)
5) Isothermal (AT 0 so AE 0)
6) Adiabatic (q 0)

State Functions
Entropy (S)
Phases oI matter
AS Ior rxns
AS EnS
products
- EnS
reactants


Enthalpy (H)
Exothermic (AH0) / Endothermic (AH~0)


Bond Enthalpies AH ED
broken
- ED
Iormed

Bond breaking is endothermic Bond making is exothermic

Whatis AH Ior the Iollowing rxn?
Bond Enthalpies (kJ/mol)
12


C-H 413
C-Cl 328
Cl-Cl 242
H-Cl 431







Enthalpies oI Formation
AH EnAH
I,products
- EnAH
I,reactants

Given the Iollowing standard enthalpy of formation values, calculate the AH
rxn
oI the Iollowing reaction:
PCl
3
(g) 3HCl(g) 3Cl
2
(g) PH
3
(g)
Compound
PCl
3
(g)
HCl(g)
PH
3
(g)
AH
I
(kJ/mol)
288.07
92.30
5.40
Hess`s Law C
2
H
4
(g) 6F
2
(g) 2CF
4
(g) 4HF(g) AH ?

H
2
(g) F
2
(g) 2HF(g) AH -537kJ
C(s) 2F
2
(g) CF
4
(g) AH -680kJ
2C(s) 2H
2(g)
C
2
H
4(g)
AH 52.3kJ







Gibb`s Free Energy (G)
AG0 Spontaneous
AG~0 Nonspontaneous
AG0 At equilibrium
AG EnAG
I,products
- EnAG
I,reactants

AG AG RTlnQ
AG -RTlnK
eq




AH AS

- Spontaneous at all temperatures
- Non-spontaneous at all temperatures
- - Spontaneous at low temperatures
Spontaneous at high temperatures
AG AH - TAS






13
14
Gen Chem Day 7-Electrochemistry

Oxidation loss oI electrons LEO OIL
Reduction gain oI electrons GER RIG

Oxidation States
1) Elements in their elemental Iorm are in the zero oxidation state.
2) Group 1 metals are 1 and Group 2 metals are 2.
3) Hydrogen is 1 except when bonded to metals (when it`s 1).
4) Transition elements must be determined by context (except Al3, Zn2, Cd2, Ag1)
5) The most electronegative elements get their typical oxidation state.
6) The last element not assigned balances the charge oI the compound/ion.

Balancing Redox Rxns
MnO
4
-
(aq)
I
-
(aq)
Mn
2
(aq)
I
2(s)













Oxidizing Agent (Oxidant) species that is reduced
Reducing Agent (Reductant) species that is oxidized
Elements or compounds are oxidized/reduced whereas only compounds act as reducing/oxidizing agents).


Electrochemical Cells
a) The anode is always the site oI oxidation (an ox)
b) The cathode is always the site oI reduction (red cat)
c) Electrons always Ilow Irom anode to cathode
d) Anions Ilow to the anode and cations to the cathode through the salt bridge
e) In the galvanic/voltaic (spontaneous) cells, the cathode is and the anode is
The signs are the opposite in electrolytic (non-spontaneous) cells.
I) For metal/metal salt solution cells, the cathode gains mass, while the anode loses mass.

Standard Cell Ptoentials (c c
cat
- c
an
c c
red
c
ox
)
Remember that the standard hydrogen electrode (SHE) has a potential oI 0.00V

Al
3
3e
-
Al -1.66V
Mn
2
2e
-
Mn -1.18V
Zn
2
2e
-
Zn -0.76V
Cr
3
3e
-
Cr -0.74V
Fe
2
2e
-
Fe -0.44V
Co
2
2e
-
Co -0.28V
Ni
2
2e
-
Ni -0.25V
2H

2e
-
H
2
0.00V
Cu
2
2e
-
Cu 0.34V
A




Non-standard cell potentials
15
Q
n
E E log
0592 . 0
=
(Nernst Equation)
Know the qualitative eIIects that will result in a higher/lower potential.
1) ShiIt to the right higher potential
g

1e
-
Ag 0.80V
2) ShiIt to the leIt lower potential


Reduction potentials
a) What is the strongest oxidizing agent?
b) What is the strongest reducing agent?
c) Which pairs will react spontaneously?


Spontaneous Rxns
AG 0
E
cell
~ 0
Q K


Electrolysis
Na

1e
-
Na -2.71V 2Br
-
Br
2
2e
-
-1.07V
2H
2
O 2e
-
H
2
2OH
-
-0.83V 2H
2
O O
2
4H

4e
-
-1.23V

a) What are the products oI electrolysis oI NaBr
(l)
?

b) What are the products oI electrolysis oI a solution oI NaBr?


Quantitative Calculations

(Amps)(T
s
)(MW) g product (Amps)(T
s
) moles product
(n)(F) (n)(F)