Beruflich Dokumente
Kultur Dokumente
ATOMIC THEORIES
EARLY THEO RY
DALTON Billiard ball: law of defi nite composition, laws of multiple proportions, law of conservation of
mass
THOMSON Raisin bun: with cathode rays, found electric charge in matter; negative ELECTRONS in
positive core
RUTHERFORD Planetary: some radiums particles shot at gold foil deflected; atom is mostly empty
with positive PROTONS in small, centre NUCLEUS
CHADWICK because of isotopes, there are neutral NEUTRONS
QUANTUM THEO RY
MAXWELL light = an ELECTROMAGNETIC wave of electric & magnetic fi elds, exerting forces on charged
particles
PLANCK electromagnetic radiation travels in QUANTA (bursts of energy); photons are quanta of light
energy
BOHR improved Rutherfords; explained orbiting electrons dont lose energy and collapse, and atomic
spectra
1. STATIONARY STATE - each orbit means a state of constant energy.
2. TRANSITION STATE - electrons change their specifi c energy quanta. An electron gains a quantum of
energy, moving to a higher energy state, and returns, emitting a photon.
DE BROGLIE electron particle acts like a WAVE
SHRODINGER wave equations, proposing QUANTUM MECHANICS
HEISENBERG UNCERTAINTY PRINCIPLE: impossibility of knowing position and velocity of electrons
DENOTATION
Main energy level
EVIDENCE
Low-res line spectra
VALUES
Period #; d-1, f-2
(# of e - = 2n 2 )
n-1, to 0
2. l, azimutal
3. m l , magnetic
Orbital orientation
-l to +l
4. m s , spin
Electron spin
+ or -
(up or down)
Spectra in magnetic
fi eld
Ferro/paramagnetism
ORBITAL SUBSHELL
1. s, sharp
2. p, principle
3. d, diff use
4. f, fundamental
ORBITAL SHAPE
0, sphere
1, dumbbell
2, double dumbbell
3, fl ower
NUMBER OF ORBITALS
1
3 (p x , p y , p z )
5
7
# MAX ELECTRONS
2
6
10
14
AUFBAU PRINCIPLE add electrons at the lowest energy orbital; problems with building up properly
HUNDS RULE add one electron to all orbitals in same subshell before doubling up; problems with
spacing/random wrong spin
PAULI EXCLUSION PRINCIPLE electrons in one orbital have opposite spins; no same set of quantum
numbers; problems with same spin in same box
ENERGY LEVEL
DIAGRAM
Fluorine
ENERGY
2s
1s
2p x
2p y
2p z
ELECTRON CONFIGURATION
ENTITY
Normal atoms
Normal metals (Zn, Mn, Ag, Pb)
Unusual metals (Cu, Cr, Mo, Ag, Au)
* stability/lower energy with
and all fi lled d-orbitals
ATOM CONFIGURATION
O [He] 2s 2 2p 4
Zn [Ar] 4s 2 3d 10
ION CONFIGURATION
O 2- [He] 2s 2 2p 6
Zn 2+ : [Ar] 3d 10
Cu: [Ar] 4s 1 3d 10
Cu + : [Ar] 3d 10
MAGNETISM
- Unpaired electrons align to a magnetic fi eld, causing attraction
DIAMAGNETIC no attraction individual atoms with no unpaired electrons
PARAMAGETIC weak attraction individual atoms with unpaired electrons
FERROMAGNETIC strong attraction Fe, Co, and Ni have unpaired electrons, but are also small and
tightly packed; when magnetized, each atom of a large collection/domain face the same orientation
S U P E R C O N D U C T O R S a l l o w re s i s t a n c e f re e t r a n s m i s s i o n o f e l e c t r i c i t y a t u p t o 1 5 0 K
BONDING
INTRAMOLECUL AR FO RCES
LEWIS STRUCTURES for ionic or covalent compounds, atoms form chemical bonds to achieve a stable
octet of electrons (valence electrons = electrons in orbitals of highest energy level)
1. Arrange atoms symmetrically, around the atom of lowest EN.
2. Of the total valence e - , put 2 per bond between the central and surrounding atoms, then the rest as
lone pairs around the atoms.
3. Create double/triple bonds to remove FORMAL CHARGE (atoms valence 2 per lone pair 1 per
bond pair) and allow C, N, O and F to follow the OCTET RULE.
4. Add brackets and charge if polyatomic; add if resonance occurs.
VSEPR SHAPES for covalent and polyatomic ions, maximum valence electron repulsion predicts shape
angles.
MOLECULES.
HYBRIDIZATION decreases energy of bonding atoms; promotes e - to vacant orbitals and then hybridizes
to form overlapping orbitals; the 2 electrons of opposite spin are between both nuclei
ELECTRONEGATIVITY measure of nucleis attraction of electrons; increases left to right (more protons,
more nuclear charge) and bottom to top (less shielding, less distance from nuclei)
[pure covalent]
0
increasingly polar
[ionic]
1.7
increasingly ionic
4.2
IONIC BOND electrostatic attraction between anions and cations in a crystal lattice; net energy
decreasewhen released lattice energy exceeds cations ionization energy and anions electron affi nity
COVALENT BOND electron sharing; balances electrons attraction to nuclei and repulsion to other
electrons
INTERMOLECUL AR FORCES
- explains melting and boiling points, and solubility
LONDON DISPERSION e - instant attraction to nuclei for ALL molecules; increases with # ELECTRONS and
ATOMS
DIPOLE-DIPOLE attraction between oppositely charged ends of polar molecules
HYDROGEN BONDING strong dipole-dipole between H F/O/N
PROPERTIES OF SOLIDS
TYPE OF SOLID
Ionic crystal
Metal + non-metal
ions
FORCES
Ionic bond
PROPERTIES
- Hard; brittle (crystal)
- High melting point (strong
ionic)
- Conducts as liquid/aq (ions)
EXAMPLES
NaCl
Metal
Metal + metal
cations
Metallic bond
* low IE loosely held e - e sea in
vacant orbitals +ve kernel &
conductivity
- Soft-hard
- Ductile, malleable, lustrous
- Conducts as solid/liquid
(free e - )
Pb, Fe, Cu
Molecular
Nonmetal +
nonmetal
- Soft
- Low melting point (weak
IMFs)
- Nonconducting (neutral)
H 2 0, CO 2
Covalent network
Molecule + molecule
C, SiC, SiO2,
B, As, Sb, Bi,
Po
// ENERGY CHANGES //
THERMOCHEMISTRY
CHANGES IN MATTER AND ENERGY
BOUNDARY separates system and surroundings
THERMAL ENERGY kinetic energy from vibration, rotation, translation of molecules
HEAT (q) amount of energy transferred between substances
TEMPERATURE (T) average kinetic energy of particles
HEAT
q = mcT
m = mass, g
c = specifi c heat capacity, c w = 4.18 J/(gC)
T = change in temperature, C
ENTHALPY CHANGE
Physical
Chemical
Nuclear
EFFECT
Intermolecular forces
Chemical bonds (structure)
Nuclei (protons & neutrons)
EXOTHERMIC
ENDOTHERMIC
Enthalpy Diagram
A(aq) + B(aq)
Potentia
l energy
H
1 - 10 2 kJ/mol
10 2 - 10 4 kJ/mol
10 10 10 12 kJ/mol
H = - 100
kJ
Enthalpy Diagram
A(aq) + B(aq)
Potentia
l energy
AB(aq)
H = + 100
kJ
AB A + B, H = + 100 kJ/mol
AB + 100 kJ A + B
CALORIMETRY process of measuring energy changes (assumes: no heat between in & outside; negligible
heat by materials; dilute aq. solution has density and heat capacity of water)
FIRST LAW energy is constant, neither created nor destroyed, but can be transformed
ENTHALPY CHANGE (H) diff erence in total value of a systems energy
H = q, under SATP (25C, 100 kPa)
state function (path independent)
HESS LAW OF HEAT SUMMATION standard enthalpy of an ultimate reaction is the same for the sum of
its steps
nH x = H t o t a l
nH x = mcT
H
qwater
* from calorimetry; c=4.18
1. ONE MOLE OF REACTANT
H = nH f (products) - nH f
(reactants)
CHEMICAL KINETICS
HOMOGENEOUS all molecules in same state/phase
as [R] , [P] ; rate of [R] progressively declines
measured by: mass change; volume/pressure changes of gas products; resistance for electrical
conductivity of solution; titration for concentration change; precipitate for absorption of light
FACTORS OF RATE
- r collision frequency x fraction of effective collisions
- reactant molecules must have proper orientation
THRESHOLD ENERGY minimum kinetic energy to convert KE to E a , during activated complex
ACTIVATION ENERGY - minimum kinetic energy to react, overcoming repulsive forces of nuclei and eclouds, creating the activated complex
MAXWELL-BOLTZMAN DISTRIBUTION probability of molecules with enough kinetic energy to
successfully collide
EFFECT
Collision frequency
FACTOR
Concentration
Surface area
Temperature
Chemical nature of reactants
EXPLANATION
More reactant available
More reactant in contact
More kinetic energy (x2 for 10C)
Individual reactivity increases when:
high EN
weak bonds; low E a /threshold
energy
few bonds, unspecifi c geometry
Typically lowers activation pathway
More kinetic energy
Catalyst
Temperature
RATE L AWS
RATE OF REACTION
r = c/t
r A r B
c = change in concentration, mol/L
t = change in time, s
ORDER OF REACTION
r = k[X] m [Y] n
k = rate constant, from data
[X] m = concentration of X, to the rate law exponent
ARRHENIUS EQUATION
k = Ae (-E a /RT)
k = rate constant
A = constant, of frequency factor
E a = activation energy, J
R = gas constant, 8.31 J/(molK)
T = temperature, K
REACTION MECHANISMS
ELEMENTARY STEP step in a reaction mechanism (an overall reaction) involving one, two, or three
particles
exponents in rate law predicted to be stoichiometric coeffi cients
RATE-DETERMINING STEP slowest elementary step that limits the reaction rate
faster steps BEFORE this determines concentration of slowest step
REACTION MECHANISM
Rate-determining
step
An activated
complex
Potentia
l energy
Ea
An
intermediate
Ea
(reverse)
// EQUILIBRIUM //
CHEMICAL SYSTEMS
DYNAMIC EQUILIBRIUM forward and reverse reactions occurring at the same rate, so their eff ects
cancel ()
PERCENT REACTION < 1% = no rxn, <50% = reactants favoured, >50% = products favoured, >99% =
quantitative rxn
EQUILIBRIUM
Solubility
EXPLANATION
In a saturated solution,
rate of dissolving = rate of crystallizing
EXAMPLE
Amount of excess solute in solution
remains constant
Phase
In a closed system,
rate of condensation = rate of evaporation
Chemical
In a chemical reaction,
rate of reverse = rate of forward reaction
L AWS OF THERMODYNAMICS
FIRST LAW energy is constant & conserved
SECOND LAW all changes increase the entropy of the universe
most spontaneous rxns: exothermic (H; heat released) & increased entropy (+S; more
chaos)
S increased by: more moles; (s) (l) (aq) (g); more volume; more temperature
a systems entropy decreases at the expense of the universe (heat goes to surroundings)
THIRD LAW S=0 at T=0 K
like H, S is a state function at SATP (a.k.a use known values to calculate)
ENTROPY
S = nS (products) - nS (reactants)
G = H TS
T = temperature, in K
G & S = values from reference
SPONTANEITY
Spontaneous
G
()
H
()
()
(+)
Non-spontaneous
(+)
(+)
At equilibrium
TS
(+) = very () at all temps
() = only () at low temps
(+) = only () at high temps
() = (+)
EXAMPLE
Substance AB has an initial concentration of 2 mol/L, and an
equilibrium concentration of 1 mol/L. What are [A 2 ] and [B 2 ]
at equilibrium?
2AB 3
I ni tial
C hange
2 M
A2
0
-2x
+x
+3x
* reactants =
* products = +
* eqn
coeffi cients
E quilib rium
* from I C
[A] a [B] b
K < 1 (more
reactants)
K > 1 (more
products)
* Only
(g) &
(aq)
REACTION QUOTIENT
Therefore at
equilibrium,
[A 2 ] = x =0.5 M
[B 2 ] = 3x = 1.5 M
= 1 M
K = [B 2 ] 3
6.8 = (3x)
(2-2x) 2 (x)
x = 0.5 M
Q = [C] c [D] b
Q < K (to products)
Q > K (to reactants)
Q = K (equilibrium)
3x
1 = 2 2x
x = 0.5 M
Therefore at equilibrium,
[AB 3 ] = 1 M, [A 2 ] = 0.5 M, [B 2 ] = 1.5 M
[A] a [B] b
3B 2
[AB 3 ] 2 [A 2 ]
K = [C] c [D] b
2 2x
* Only
(g) &
(aq)
EXAMPLE
If K sp = 8.5E-9, what is the molar solubility of AB 2 in water?
AB 2(s) A + (aq) + 2B - (aq)
ni tial
I
0
0
E qui lib
2x
K = [A + ][B - ]
Q < K (to products)
Q > K (to reactants)
Q = K (equilibrium)
* Only
(aq)
K = [A + ][B - ]
8.5E-9 = x(2x)
x = 1.3E-3
Therefore,
molar solubility is 1.3E-3 M.
* Only
(aq)
Common ion eff ect - another salt with a common (aq) ion
contributes to initial concentrations
If 0.05 L of 0.001 M X and 0.05 L of 0.01 M Y mix in solution,
AB 2 is the predicted solid precipitate. K sp is 3E-2. Will the
precipitate form?
AB 2(s) A + (aq) +
2B - (aq)
n
0.00005
0.0005
mol
mol
=C 1 V 1
Q = [A + ][B - ]
V total
C2
=n/V t
0.10 L
0.0005 M
0.005
M
Q = (0.0005)(0.005)
Q = 2.5E-6
Therefore, since Q < K sp ,
no precipitate forms.
Increased pressure
Halved volume
2A 3B +2 C
Increased concentration
DEPENDS ON
COEFFICIENT
Added catalyst/inert gas
[reactant] or [product]
SHIFT
To side without energy
* aff ects K
To side of fewer total coeffi cient moles
* (g) only
* no eff ect if same # moles
To opp side of , or same side of
Adding MnO 2 or Ne
NO EFFECT
Concentration
FACTOR
Increased temperature
Pr o d u c t
Re a c t a n t 1
Re a c t a n t 2
Pr e s s u r e
[R2]
Vo l u m e
Te m p
[P]
ACID
Produce H+
Donate H+
Accept electron pair
BASE
Produce OHAccept H+
Donate electron pair
STRONG ACID completely ionizes = dissociates; strong acid = weak conj base; high conductivity
AMPHOTERIC strong acids able to donate or accept a proton; e.g. H 2 0
CONJUGATE PAIRS acid H + = conj base; base + H + = conj acid
pH measured by: pH meter; pH paper; indicators (weak acids in equilibrium); conductivity
PERCENT IONIZATION ([H+] from pH / initial M) x 100%; decreases as [reactant] increases
EXAMPLE
[H + ] = 10 - 2. 38 = 4.2e-3
HA
I
0.100 M
0
H+
0
- 4.2e-3
+ 4.2e-3
+ 4.2e-3
0.096
4.2e-3
4.2e-3
AK a = [H + ] [A - ]
[HA]
K a = 1.8e-4
Therefore,
HA is a weak
acid.
B + H 2 0 (l)
BH + + OH -
EXAMPLE
NaCl, KNO 3 , NaI
pH
Neutral
NaF, KC 2 H 3 O 2
Basic
NH 4 Cl
Acidic
NH 4 F
Acidic, if K a greater
Basic, if K b greater
AlCl 3 , FeCl 3
Acidic
Metal oxides
CaO + H 2 0 Ca 2+ + 2OH -
Basic
Nonmetal oxides
CO 2 + H 2 0 H + + HCO 3 -
Acidic
ACID-BASE TITRATION
TITRATION adding titrant from buret to a sample in Erlenmeyer fl ask to reach both the endpoint
(indicator changes colour) and equivalence point ([H + ] = [OH - ]; stoich moles are equivalent)
e.g. Calculate the pH of the resulting solution after 20 mL of 0.2 M NaOH has been added to 25 mL of 0.2 M
acetic acid.
HC 2 H 3 O 2
C2H3O2
( aq)
OH - ( aq)
H20
(l)
After n
0.001
V total
0.045 L
C2
=n/V total
0.022 M
0.004
0.089 M
(aq)
Before
n
=C 1 V 1
0.2(0.025)
= 0.005
mol
0.2(.02)
= 0.004
mol
(LR)
Change
n
- 0.004
- 0.004
+ 0.004
HC 2 H 3 O 2 (aq)
I
0.022
C
- x
H+
0
( aq)
C2H3O20.089
K a = [H + ] [C 2 H 3 O 2 - ]
( aq)
[HC 2 H 3 O 2 ]
1.8e-5 = x(0.089+x)
+ x
+ x
0.089 +
x
(0.022-x)
E
0.022 x
x = 4.4e-6 = [H + ]
pH= -log[H + ] = 5.35
TITRATION CURVE
pH
Vo l u m e o f N a O H a d d e d
BUFFER SOLUTIONS
BUFFER WEAK ACID & SALT OF CONJ BASE, or WEAK BASE & SALT OF CONJ ACID; e.g. HC 2 H 3 O 2 + NaC 2 H 3 O 2
no pH changes: added base shifts right but replaces H 3 O + ; added acid shifts left but reacts with
+
H3O
HENDERSON-HESSELBALCH EQUATION
pH = pKa + log [A - ]
[HA]
e.g. A buff er solution is made by 0.1 L of 2 M acetic acid to 0.1 L of 1 M NaOH. What is the [H + ]
concentration of the buff er?
HC 2 H 3 O 2
C2H3O2
Befor
e n
=C 1 V 1
(aq)
OH - ( aq)
H20
(l)
K a = [H + ] [C 2 H 3 O 2 - ]
[HC 2 H 3 O 2 ]
(aq)
0.1(2)
= 0.2 mol
0.1(1)
= 0.1 mol
(LR)
etc
Chang
e n
- 0.1
- 0.1
+ 0.1
After
n
0.01
0.1
V to tal
0.2 L
C2
=n/V tot
0.05 M
0.5 M
al
HC 2 H 3 O 2
0.05
- x
+ x
+ x
0.05 x
0.5 + x
(aq)
H+
( aq)
+
0.5
C2H3O2-
(aq)
// ELECTROCHEMISTRY //
ELECTRIC CELLS
REDOX
REDOX REDUCED (gain e-, O.A, + at cathode GERC) & OXIDIZED (lose e-, R.A, at anode LEOA)
OXIDATION STATES the charge or valence on the entity; 0 for neutral atoms and pure covalent
ELECTRON TRANSFER for synthesis, decomposition and single displacement reactions
BALANCING REDOX to fi nd # of electrons lost/gained
1. Split equation into half reactions. (entity changed entity; one equation per product)
2. Balance atoms other than O and H.
3. Balance O by adding H 2 O.
4. Balance H by adding H + .
5. Balance net charge by adding e - .
6. Make # of e- equal; add half-reactions; cancel entities on both sides.
7. IN BASIC SOLUTIONS Add the same # of OH - to both sides as there are H + present.
8. Combine H + and OH - into H 2 O; cancel entities on both sides.
CORROSION iron + oxygen + water; iron as anode (iron oxidized) and cathode (oxygen + water
reduced); by acid, stress
COATING appearance & protection (more easily oxidized/corroded; sacrifi cial anode)
ELECTROCHEMICAL CELLS
ELECTRIC CELL converts chemical potential energy into electrical energy; connected in a series for a
battery
STANDARD NOTATION lists cathode fi rst; cathode (+) Ag (s) | Ag 2 SO 4(aq) || CuSO 4 | Cu (s) anode (-)
GALVANIC CELL
Electron fl ow
V
Cathode (+):
Ag
Anode (-): Sn
Salt bridge
(neutrality)
cation Sn 2+
Ag + anion
n e- = IT/F
n e- : n x
* F = 96500 C/mol
CALCULATION
E cell indicates the cell potential
at ion concentrations of 1 M and
SATP.
STANDARD CELL POTENTIAL
E cell = E r ed - E ox
E cell = -0.0592 logK
n eEcell > 0
(spontaneous)
E cell indicates the cell potential
at DIFFERENT ion
concentrations.
CELL POTENTIAL
E cell = E cell - 0.0592 logQ
n e-
EXAMPLE
What is the standard cell potential of: Sn + 2Ag + Sn 2+ +
2Ag?
Reactants
Sn (s)
Ag + (aq)
H2O
H O
* (l)
(aq) = H 22O (l )
Agent
SRA
SOA
OA
RA
E r (V)
+0.14
+0.80
-0.83
+1.23
SOA/Cathode:
2Ag + + 2e - 2Ag
SRA/Anode:
Sn Sn 2+ + 2e 2Ag + + Sn Sn 2+ + 2Ag
E r = +0.80V
E r = +0.14V
E r = +0.94V
// ORGANIC CHEMISTRY //
FUNCTIONAL GROUPS
Group
Structure
Name priority
Carboxyl
ic acid
CH 3 -CO-OH
Ethanoic acid
Ester
CH 3 -CO-O-CH 3
Methyl
ethanoate
Prefi x
group
Properties
Reactions
- polar
- LDF, d-d, Hbond
- soluble
- polar
- LDF, d-d, Hbond
- soluble if small
Oxidation (KMnO 4 )
Aldehyde + O carboxylic
acid
Condensation (H 2 SO 4 & )
Carb acid + alcohol ester +
H2O
Saponifi cation
Ester + NaOH Na-acid +
alcohol
Amide
CH 3 -CO-N-H 2
Ethanamide
Aldehyd
e
Ketone
CH 3 -CO-H
CH 3 -CO- CH 3
Ethan-#-al
Propan-#-one
#-oxo
#-oxo
- polar
- LDF, d-d, Hbond
- soluble
- polar
- LDF, d-d
- soluble
Oxidation (KMnO 4 /K 2 Cr 2 O 7 )
1 alcohol aldehyde + H 2
2 alcohol ketone + H 2
3 alcohol degrades
Alcohol
CH 3 -OH
Ethan-#-ol
#-hydroxy
- polar
- LDF, d-d, Hbond
- soluble
Reduction (Ni/Pt)
Aldehyde + H 2 1 alcohol
Ketone + H 2 2 alcohol
Dehydration (H 2 SO 4 & )
Alcohol alkene + H 2 O
Amine
CH 3 -N-H 2
Ethan-#-amine
#-amino
Alkene
Alkyne
Alkane
Halide
Benzene
CH 2 =CH 2
CH= CH
CH 3 -CH 3
CH 3 -Cl
Eth-#-ene
Eth-#-yne
Ethane
#-ethyl
Benzene
#-chloro
#-phenyl
- polar
- LDF, d-d, Hbond
- soluble
- nonpolar
- LDF
- non-soluble
Substitution
H
Br
H-C-H + Br 2 H-C-H
H
H
Addition
Br Br
H-C=C-H + Br 2 H-C-C-H
H H
* Markovnikovs rule
(C with more Hs gets H)
Substitution
+ Br 2
+ Br 2
-Br + HBr
-Br
-Br
Ether
*
*
*
*
CH 3 - CH 2 -OCH 3
methoxyethan
e
- polar
- LDF, d-d
- soluble
Condensation (H 2 SO 4 )
R-OH + HO-R R-O-R + H 2 0
H 2 SO 4 C=C
[O] in KMnO 4 /K 2 Cr 2 O 7 C=O CO-OH
boiling pt/polarity: alkane ether amine aldehyde ketone alcohol carb acid amide
addition polymer contain at least one double bond; nylon contains crosslinking for fl exibility