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Dr. Sun
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Dr. Sun Chemistry Summary .
CONTENTS
Chapter Page
Chapter 01 Atoms and Periodic Table 03
Chapter 02 Chemical Bond and Molecular geometry 11
Chapter 03 Name Compounds and Ions 18
Chapter 04 Liquid , Solid and Intermolecular Force 20
Chapter 05 Gases 23
Chapter 06 Solutions 25
Chapter 07 Stoichiometry 28
Chapter 08 Chemical Reactions 30
Chapter 09 Kinetics 36
Chapter 10 Chemical Equilibrium 40
Chapter 11 Acids and Bases 42
Chapter 12 Electrochemistry 48
Chapter 13 Thermodynamics 53
Chapter 14 Nuclear Chemistry 55
Chapter 15 Organic Chemistry 58
Chapter 16 Coordination Chemistry 62
Chapter 17 Experimental Chemistry 66
Chapter 18 Units and Significant Figures 71
Chapter 19 Overview 73
proton 1 amu +1
matter molecule atom
water H2O H, O neutron 1 amu 0
electron 1
amu -1
1840
an atom
Isotopes Allotropes
Same element Same element
Different number of neutrons Different structures
C-12 and C-13 Diamond, Graphite and C60
O-16 and O-18 O2 and O3 ; S4 and S8
H-1(hydrogen), H-2 (deuterium), H-3 (tritium) P4 (white) and P1000 (red)
O
O O O O
2p
n=2
3) Hund’s Rule: Electrons fill empty orbital first if they have 2s
the same energy. If there are 3e in three p orbitals,
1s energy level n = 1
each p orbital has 1 electron.
9. Valence Electrons
Look electron configuration of oxygen: 1s2 2s2 2p4 . There are 6 electrons in energy level 2.
Electrons in the outermost energy level are valence electrons. Oxygen has 6 valence electrons.
period and the column is called group. There are 7 periods and 8 main group(A groups) and 10 transition groups
( B groups).
1A Alkali metals 1 active metals (except H), always lose 1e to form M+1 when react
with nonmetals.
2A Alkaline earth 2 less active than group 1, always lose 2e to form +2 ions.
metals
3A Metalloid 3 B is metalloid. Al is a common metal to form +3 ions.
Metals Other are metals
4A Nonmetal 4 C is nonmetal and forms four bonds with nonmetals.
Metalloid Si is metalloid and used in making computer chips.
Metal Pb is metal.
5A Nonmetal to 5 N, P are nonmetals; As, Sb are metalloids; Bi is metal.
metalloid to metal
6A Nonmetal to 6 O, S, Se are nonmetals; Te is metalloids; Po is metal.
metalloid to metal
7A Halogens 7 F always get 1e. Cl, Br, I gain 1e when react with metal, lose
Active nonmetal electrons when react with oxygen and can be +1, +3, +5, +7.
8A Noble gas 8 They are not active. Rarely react with F and O.
B Transition Metals 1-2 They can form +1, +2, +3, +4, +5, +6, +7 ions.
group Because d orbitals can be involved to form bond.
Rare earth metals Lanthanide Series and Actinide Series
Diatomic elements H2, N2, O2, and halogen F2, Cl2, Br2, I2
Monoatomic elements All noble gases
2 liquid elements Br2 (purple), Hg (shining liquid metal)
11 gas elements H2, N2, O2, F2, Cl2 and noble gas.
increase decrease
decrease
Electronegativity increase Atomic radius
Ionization Energy
2) Each element has its own spectrum, which can be used to identify the element.
1. Coulomb Law:
Like charges repel and unlike charges attract. This is the only force to understand atoms to form molecules and
molecules to form solids and liquids.
2. Chemical Bond
1) Chemical bond is the force between atoms. Protons in one atom attract electrons in another atoms.
2) Bond Energy = the energy required to breaking a bond. Formation of a bond always release energy. For
example, H + H = H2 + 436 kJ/mole, which means formation of H2 release 436 kJ/mole. Breaking H-H bond
requries 436 kJ/mol. When a system releases energy, it becomes more stable. If the bond energy of a bond is
higher, the bond is stronger.
3) Bond length: Distance between two bonded atoms. Bond length of H-H is 74 pm. 1pm = 1 x 10-12 m.
4. Octet Rule - Atoms tend to have 8 electrons in its valence shell ( outermost shell).
Atoms can lose, gain or share electrons to have 8 valence electrons. This rule is useful to understand bond
formation. For example, when Na meets Cl, Na loses 1e and Cl gains 1e, then both have 8e in valence shell.
Generally, X < 0.5 = nonpolar bond; 0.5 ≤ X ≤ 1.8 = polar bond; X > 1.8 = ionic bond.
Where X = electronegativity difference of atoms A and B.
When X is larger, bond is more polar.
Polarity is measured by dipole moment (µ) = Q.d Q = charge d = distance between two charges.
Unit of dipole moment: Debye (D) = 3.34 x 10-30 coulomb.meter. For example, µ of H-F = 1.91D
9. Resonance Structures
A. Resonance structures: are two or more Lewis structures for one molecule or ion.
B. Why we need to write resonance structures: For some molecules, say SO3 (see below), a single structure
cannot represent its real structure. Look at the Lewis structure below, it has one S=O bond, two S-O bonds. But in
reality, three S-O bonds have the same bond length. So this Lewis structure is not right. How to write a correct one?
You write three structures! The real structure is the average of the three structures. Then the bond order of each S-
O is 4/3 = 1.33. Can bond order be a fraction? Yes.
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C. How to draw resonance structures: change the position of double bond but don’t touch atoms. If you can
draw two or more resonance structures, the one satisfying octet will mostly represent the real structure
O O O
S S S
O O O O O O
Three resonance structures of SO3
H2O O H NH3 H N H CO C O
H H
O C O O S
CO2 O3 SO2
O O O O
-2 O F
SO3-2 O S O SO3 BF3
S B
O O O F F
Cl O -2 F
SiCl4 SO4-2 SF6 F F
Cl Si Cl O S O S
F F
Cl O F
Cl F
PCl3 Cl P Cl PCl5 Cl SF4 F
P Cl S
Cl
Cl F
Cl F
O O O
HNO3 H2SO4 HClO4
N HO S OH O Cl O H
O OH
O O
Element F O N C
Valence Electron 2s2, 2p5 2s2, 2p4 2s2, 2p3 2s2, 2p2
configuration
P orbital
Energy
H
4H
2p 2p 2p H C H
4 SP3 H
2s
C electron configuration 1) excitation 2)hybridization 3) bond formation
3) Geometry of sp3 hybrid orbital
The left picture shows the shape of one sp3 orbital and the right one shows four sp3
Orbitals with angle 109.5o . This geometry is tetrahedron.
Domain 2 3 4 5 6
Hybrid sp sp2 sp3 sp3d sp3d2
orbital
Number of 2 3 4 5 6
bonds
Molecular
Geometry
(electron pair
geometry)
Example: CO2 central atom C, it bonds to 2 atoms and has 0 electrons pairs. Domain = 2 + 0 = 2
H2O central atom O, it bonds to 2 atoms and has 2 electron pairs. Domain = 2 + 2 = 4.
SF6 central atom S, it bonds to 6 atoms and has 0 electron pairs. Domain = 6 + 0 = 6.
14. Principle of Molecular Geometry: VSEPR - Valence Shell Electron Pair Repulsion
H
Why H C H is tetrahedron rather than square planar? The angles in tetrahedron are 109.5o, while the angles in
H
N
H N H N
H H H H
H H H
Lewis Electron pair geometry Molecular geometry
Structure Tetrahedron Trigonal pyramidal
2 0 2 sp Linear
BeF2
Linear
3 0 3 sp2 Trigonal
BF3 planar
Trigonal planar
2 1 3 sp2 Trigonal
SO2 planar
Bent
4 0 4 sp3 Tetrahedron
CH4
Tetrahedron
3 1 4 sp3 Tetrahedron
NH3
Trigonal pyramidal
2 2 4 sp3 Tetrahedron
H2O
Bent
5 0 5 sp3d Trigonal
PCl5
bipyramidal
Trigonal bipyramidal
4 1 5 sp3d Trigonal
SF4
bipyramidal
Seesaw
3 2 5 sp3d Trigonal
ClF3
bipyramidal
T-shape
2 3 5 sp3d Trigonal
XeF2
bipyramidal
Linear
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6 0 6 sp3d2 Octahedron
SF6
Octahedron
5 1 6 sp3d2 Octahedron
BrF5
Square pyramidal
XeF4 4 4 6 sp3d2 Octahedron
Square planar
XeF3 -
3 3 6 sp3d2 Octahedron
T-Shape
4. More Names
HNO3 nitric acid NO3- nitrate HNO2 nitrous acid NO2- nitrite
HCN hydrocyanic acid CN- cyanide HOCN cyanic acid OCN - cyanate
HSCN thiocyanic acid SCN- thiocyanate HMnO4 permanganic MnO4- permanganate
acid
HClO hypochlorous acid ClO- hypochlorite HClO2 chlorous acid ClO2- chlorite
HClO3 chloric acid ClO3- chlorate HClO4 perchloric acid ClO4- perchlorate
HBrO3 bromic acid BrO3- bromate HIO3 Iodic acid IO3- Iodate
H3PO4 phosphoric acid H2PO4- dihydrogen HPO42- hydrogen PO43- phosphate
phosphate phosphate
H3PO3 phosphorous acid H2PO3- dihydrogen HPO32- Hydrogen PO33- phosphite
phosphite phosphate
H2CrO4 chromatic acid CrO42- chromate H2Cr2O7 dichromatic Cr2O72- dichromate
acid
Fe2O3 iron(III) oxide FeO iron(II) oxide AlCl3 aluminum Al2O3 aluminum
ferric oxide ferrous oxide chloride oxide
Cr2O3 chromium (III) oxide CrO chromium (II) oxide HgO mercury (II) oxide
Mercuric oxide
Hg2O mercury (I) oxide
Chromic oxide mercurous oxide
chromous oxide
Co2O3 cobalt (III) oxide CoO cobalt (II) oxide SnO2 tin (IV) oxide SnO tin (II) oxide
stannous oxide
cobaltic oxide cobaltous oxide stannic oxide
CuO copper (II) oxide Cu2O copper (I) oxide Ni2O3 nickel (III) oxide NiO nickel (II) oxide
nickelic oxide nickelous oxide
Cupric oxide cuprous oxide
PbO2 plumbic oxide PbO lead (II) oxide
lead (IV) oxide plumbous oxide
sublimation
fusion/melting vaporization
solid liquid gas
freezing condensation
solidification
2. Phase Diagram
You can change solid to liquid to gas by changing temperature and pressures. Phase diagram tells you the phase
of a substance at a given temperature and pressure.
1) Three regions: Left region is solid (low temperature) What is the phase of H2O at 1 atm and 50 oC?
Middle region is liquid. (Answer: Liquid)
Right region is gas (high temperature)
2) Melting point line: line ABD. Melting point of H2O is 0.00 oC at 1.0 atm and it changes when pressure changes.
3) Boiling point line: line ACE. BP of H2O is 100 oC at 1.0 atm and it increases greatly when pressure increases.
4) Triple point: solid, liquid and gas coexist. Ice, water and steam coexist only at 0.006 atm and 0.01 oC.
5) Critical point: the highest temperature a liquid can exist. Liquid water will not exist if temperature is higher
than 374 oC, no matter how high the pressure is.
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6) Phase change: With phase diagram you can predict phase change. For example, H2O at 1.0 atm, from -5 oC to
20 oC to 120 oC, it change from solid to liquid then to gas. , H2O is solid. When T increase at 1.0 atm, H2O will
changes from solid to liquid then to gas.
Potential Energy: Energy of distance. Solid < liquid < gas in PE. solid
A
water heating curve time
4. Heat Calculation
Calculate the heat absorbed when 10g H2O change from –20oC to 120oC
Process Formula Constant Energy change Note
AB Q = m.Cice.T Cice = 2.05 J/ g. C o
KE KE = kinetic energy =
BC Q = m.Hfus Hfus = 334 J/g PE Phase change, T and KE no change
CD Q = m.Cwater.T Cwater = 4.18 J/g.oC KE PE = potential energy
DE Q = m.Hvap Hvap = 2260 J/g PE Phase change, T and KE no change
EF Q = m.Csteam.T Csteam = 2.08 J/ g.oC KE
Two equations Q = m C T Q = m H for phase change
m = mass; C = specific heat capacity; Hfus = heat of fusion; Hvap = heat of vaporization T = change of T
6. Type of Solids
Solid Bond Example Electric conductivity
Molecular solid covalent Ice, dry ice (solid CO2), sugar No
Covalent network solid covalent Diamond (carbon) No
Graphite (carbon) Yes
SiO2 (, quartz, sand) No
Metallic network Solid metallic Fe, Cu Yes
Ionic network solid ionic NaCl Solid no
Crystal solid Liquid or solution yes
7. Separation of liquids
1) Separation funnel: used for insoluble liquids, such as water and petrol.
2) Distillation: to separate mixture of soluble liquids with different boiling points, such as water and ethanol.
Chapter 5 Gases
Gas molecules are much more separated than liquid and solid so they have negligible intermolecule force.
Temperature determines the speed of molecules. Collision between gas molecules and container wall produces
pressure. Most useful formula is ideal gas law PV = nRT.
Kinetic energy (KE): is the energy of movement. KE 1 mv 2 , where m is mass and v is speed.
2
Kinetic energy and temperature : For idea gas KE 3
RT , all molecules have the same KE at the same T.
2
Graham Law: V 3RT the speed of a gas molecule is inversely proportional to square root of its mass.
m
This formula can be derived from the two formulas above. Small molecules move fast.
3(8.31)(298)
What is the speed of O2 at 25 oC : VO 2 3RT 482 m/s m = molar mass of O2 in kg.
m 0.032kg
What is the ratio of speed of H2 to speed of O2: R = 8.31 J/mol.K
VA mB VH 2 mO
mA m H2 32 4 H2 moves 4 times as fast as O2.
VB VO2 2 2
Diffusion: gases move from high concentration to low concentration.
Effusion: gases move out from a small hole of a container.
(P + n 2a )(V-nb) = n R T
2
4. Real gas law:
v
Real gas has intermolecular force and volume. So idea gas law needs to be amended to solve real gas problems.
Two constants a and b are introduced into idea gas law, where a is an indicator of intermolecular force, b is an
indicator of molecular volume.
5. Other forms of idea gas law: Idea gas law covers BCGCA laws.
Boyle’s law: P1V1 = P2V2 if T is constant
Charles’s law: T1 T2 if P is constant
V1 V2
Gay-Lussac’s law: P1 P2 if V is constant
T1 T2
7. Speed distribution
Chapter 6 Solutions
2. Solubility
Solubility: maximum amount of solute in 100 gram solvent. Solubility of NaCl = 36g /100g H2O at 25 oC.
Saturated solution contains maximum solute; Rate of dissolving = rate of crystallizing; It at equilibrium.
Unsaturated soution: the concentration is lower than saturated. More solute can be dissolved.
Supersaturated: the concentration is higher than saturated. How to make a supersaturated solution? Make a
hot saturated solution then cool it down. If no solid comes out, you get a supersaturated solution. It is unstable.
If you put a small crystal into a supersaturated solution, the crystal will become larger and it become a
saturated solution.
6. Colligative properties:
If you dissolve some NaCl in H2O, the following changes will occur:
1) Boiling point elevation : Tb = Kb.m.i Kb=0.52 oC/m for H2O , m = molality
2) Freezing point depression : Tf = Kf.m.i Kf = -1.86 oC/m for H2O i = number of particles
3) Lowering vapor pressure : P = PoX this is Raoult’s law
The solution satisfying Raoutl’s las is called ideal solution.
4) Osmotic pressure : V = nRT.i = MRT.i
5) i is the number of particles formed when the solute is dissolved.
C6H12O6 i=1 NaCl i=2
CaCl2 i=3 Mg(NO3)2 i=3
6) Colligative property: the changes above depend on the number of particles
rather than on the nature of the particles. For example, if you dissolve 1 mole
NaCl or 1 mole KCl, the changes will be the same. This is colligative property.
7) What is osmotic pressure: if you separate water and protein solution
by a semipermeable membrane (water can pass but protein can not), water will
move from pure water side to protein solution. This is osmosis.
To prevent osmosis from continuing, a certain pressure needs to apply
on protein solution, This pressure is osmotic pressure.
This is another way to express the concentration of a solution.
8) Example: Given a solution of NaCl (29g) in H2O (500g) with density 1.03 g/ml.
Find boiling point, melting point, vapor pressure at 25 oC, osmotic pressure of this solution. Vapor pressure of
pure water at 25 oC = 24.0 mmHg. Assume NaCl can not pass semi membrane.
Step 1: Convert 29g NaCl into 29/58 = 0.5mol; Convert 500 g into 0.5 kg;
Find volume of the solution: V = mass/density = 529/1.03 = 514 ml = 0.514 Liter.
Then m = mole/kg = 0.5 mol/0.5 kg = 1; M = mole/L = 0.5mol/0.514 L = 0.97
Mole fraction of H2O: X = mole of H2O / mole of solution = (500/18) / (500/18 + 29/58) = 0.982
Step 2: Use formulas
A. Tb = Kb.m.i = 0.52 (1)(2) = 1.04 oC. boiling point = 100 + 1.04 = 101.04 oC.
B. Tf = Kf.m.i = -1.86 (1)(2) = -3.72 oC melting point = 0 - 3.72 = -3.72 oC
C. P = PoX = 24.0 x 0.982 = 23.5 mmHg
D. V = nRT.i 0.514 = 0.5(0.082)(298)(2) = 47.5 atm
2) Find mole fraction of benzene in the vapor gas phase: XA = PA/(PA + PB)
Xbenzene = 32 63% Xtoluene = 19 37% note: pressure ratio = mole ratio
32 + 19 32 + 19
8. Colloid: contains particles that are large than solute (0.1-5nm) but smaller than visible solids (50-1000nm)
It is not stable and may set out.
It has Tyndall effect : light is scattered when passing through a colloid
Shown on the right, you can see the light path in colloid, not in solution.
There are several forms of colloid:
Emulsion (liquid in liquid); Foam (gas in liquid or solid);
Aerosol (liquid or solid in gas); Gel (liquid in solid);
Sol (solid in liquid or solid). Solution Colloid
Chapter 7 Stoichiometry
2. Convert amu to Gram - Mole is the key unit (amu = atomic mass unit)
1) Mass of 1 H atom = 1 amu. 1 amu = 1 gram = 1.66 10-24 gram = mass of C-12
23
6.02 10 12
23
2) Mass of 6.02 x 1023 H atoms = 6.02 10 amu = (6.02 10 )(23 1 ) gram = 1 gram .
6.02 10 23
3) mole = 6.02 x 1023 1 mole H = 1 gram 1 mole O = 16 gram
1 mole H2O = 18 gram 1 mole O2 = 32 gram
18 gram is the molar mass of H2O.
4) Avogadra number: 6.02 x 1023 mass
32g
gram
5) Number of mole =
molar mass
23
5 L 1 mole × 6.02 10 molecules = 1.34 1023 molecules
22.4 L gram 1 mole
A1: Limit reagent is a reactant that is not enough to react with the other reactant completely.
You can see that H2 given is more than needed. So H2 is excess by 5 - 0.625 = 4.375 mole. It means after the
reaction completion, there are still 4.375 mole left. H2 is excess therefore O2 is limiting reagent.
A2: Use the limiting reagent to calculate the product. Use coefficient to set up a ratio.
10/32 = x 18 g
x = H 2 O produced = 0.625 mole = 11.25 g This is theoretical yield (calculated yield)
1 2 mol
actually collected
A3: Experimental yield = 9.5 100% 84.4%
theoretical yield 11.25
1. Types of Reactions
1) Combination reactions A+B=C Zn + S = ZnS
2) Decomposition reactions AB = A + B CaCO3 CaO + CO2
3) Single replacement AB + C = CB + A Zn + CuSO4 = Cu + ZnSO4
4) Double replacement AB + CD = AD + CB AgNO3 + NaCl AgCl + NaNO3
5) Combustion CnHmO + O2 = CO2 + H2O C5H12 + 8O2 = 5CO2 + 6H2O
6) Acid-base reactions acid + base = salt + water HCl + NaOH = NaCl + H2O
7) Redox reactions involve electron transfer (see chapter 12)
8) Organic reactions reactions of organic compounds (see chapter 15)
4. Balance Reactions - Mass, charge and energy are conserved during a reaction
1) Write correct formula for reactants and products
2) Start with polyatomic compounds, treat polyatomic ions (e.g. NO3- ) as one unit
3) Balance elements last
4) Use fractions to balance, then multiply by Least Common Multiple.
Example: Balance C6H14 + O2 → CO2 + H2O
1) how many C on the left side? 6; so put 6 before CO2. C6H14 + O2 → 6CO2 + H2O
2) how many H on the left side ? 14; so put 7 before H2O C6H14 + O2 → 6CO2 + 7H2O
3) how many O on the right side? 19; so put 19/2 before O2. C6 H14 19 O2 6CO2 7 H 2O
2
4) multiply 2 on both side. Done. 2C6H14 + 19O2 → 12CO2 + 14H2O
34 Sulfuric acid reacts with calcium hydroxide H2SO4 + Ca(OH)2 CaSO4 + H2O
35 Ammonium chloride react with sodium NH4Cl + NaOH NaCl + NH3 + H2O
hydroxide
36 Ammonia is bubble through carbonic acid H2CO3 + NH3 NH4HCO3
solution
37 Hydrochloric acid reacts with ammonia H+ + NH3 NH4+
Lewis Acid + Lewis Base Coordinate complex
38 Boron trifluoride reacts with ammonia BF3 + NH3 F3B-NH3
39 Boron trifluoride reacts with phosphine BF3 + PH3 F3B-PH3
40 Aluminum chloride reacts with phosphine AlCl3 + PH3 Cl3Al-PH3
41 Commone Lewis Acid BF3, BH3, because they have empty
AlCl3 orbital to accept electrons.
42 Commone Lewis base NH3, PH3, PCl3 because they have electron
pairs to donate to acids.
Salts (CO32-, S-2) react with strong acids (HCl, H2SO4) gas (CO2, H2S)
43 Hydrochloric acid is added to sodium CO32- + 2H+ CO2 + H2O
carbonate solution
44 Hydrochloric acid is added to sodium sulfide S2- + 2H+ H2S
solution
F2 (Cl2, Br2) + Cl- ( Br- , I-) (single replacement, redox) Cl2 ( Br2, I2)
47 Fluorine reacts with sodium chloride F2 + 2Cl- 2F- + Cl2
solution
NH3, Cl-, CN-, OH-, SCN- + transition metal ions (Zn2+, Ag+, Fe2+3+, Cu2+, Ni2+) complex ions
57 Combine with 1 ligand: Cu2+ + SCN- Cu(SCN)+
Potassium thiocyanate solution is added to
copper(II) solution
58 Potassium thiocyanate solution is added to Fe3+ + SCN- Fe(SCN)2+ (red)
iron (III) solution
Nonactive metal (Cu, Ag, Au) + oxidizing acid (H2SO4, HNO3) redox reaction
73 Copper metal is placed in concentrated Cu + 2H2SO4 CuSO4 + SO2 + 2H2O
sulfuric acid
74 Copper is placed in dilute nitric acid 3Cu + 8HNO3 3Cu(NO3)2 + 2NO + 4H2O
75 Silver is placed in concentrated nitric acid Ag + 2H +
+
NO3- Ag+ + NO2 + H2O
76 Gold is placed in a mixture of concentrated Au + HNO3 + 3HCl AuCl3 + NO + 2H2O
nitric acid and hydrochloric (1:3 molar ratio) Aqua regia dissolve gold
Metal oxide and nonmetal oxide salt
76 Solid calcium oxide powder mixed with hot CaO + SO3 CaSO4
sulfur trioxide gas
77 Solid calcium oxide powder mixed with hot CaO + CO2 CaCO3
carbon dioxide gas
Read 10 times!
5. Concentration and Rate [C] rate High concentration = more collision = high rate
1) Half-life T1/2: the time required for half reactnts to change. Only 1st order has a constant T1/2
3 day 3 day 3 day 3 day
If 32g 16 8 4 2 g, then T1/2 = 3 days
t / T1/2
2) Nt = No 1 Nt = N at time t; No = N initial; t = time; T1/2 = half-life
2
3) Example: Given the following data, a. Determine the rate law. b. Calculate the rate constant. C. Find [C4H6] at
time 4000s.
2C4H6 (g) → C8H12 (g)
Time (s) [C4H6](M) 10-2 ln[C4H6] 1/[C4H6]
0 1.73 -4.06 58
900 1.43 -4.25 69
1800 1.22 -4.41 80
3 700 0.96 -4.65 105
6000 0.72 -4.91 137
a. Plot [C4H6], ln[C4H6] and 1/[C4H6] versus time. As the plot of 1/[C4H6] versus time is straight line, the reaction
is second order. b. Rate constant k = slope of the straight line. c. At 4000s, [C4H6] = 0.0091M.
Which is a line: Not zero order not first order it is 2nd order
Arrhenius Equation k Ae Ea / RT
ln k Ea ( 1 ) ln A The graph of ln k vs. 1/T is a line with slope -Ea/R and y-intercept lnA .
R T
k
ln 2 Ea ( 1 1 ) With two experimental K and T, you can determine Ea of the reaction.
k1 R T1 T2
K: rate constant in rate law A: frequency factor
Ea: activation energy R: gas constant 8.31 J/k.mol
T: temperature in Kelvin e: constant = 2.718
9. Surface Area If a solid has larger surface area, the reaction is faster.
Potential Energe
(A)-potential energy of reactants (B)
(B)-activation energy of forward reaction (C)
(E)
1) The slowest step determines the rate law. Step B → P is the rate-determining step.
2) B is an intermediate, which is neither reactants nor products.
3) Example: Given the mechanism of a reaction on the right.
Q1. What is the overall reaction? 2NO = N2O2 (fast)
Q2. What are the intermediates?
Q3. What is the rate-determining step? N2O2 + H2 = N2O + H2O (slow)
Q4. What is the order of the reaction? N2O + H2 = N2 + H2O (fast)
A1. Add the three elementary reactions, N2O2 and N2O are canceled. 2NO + 2H2 = 2H2O + N2
A2. N2O2 and N2O are intermediates.
A3. The second step is the rate-determining step, because it is the slowest step.
A4. a. Write the rate law according to the slow step: r = k[N2O2][H2]
[N O ]
b. Express N2O2 in term of NO and Keq of step 1. K eq 2 22 then [N 2 O 2 ] = K eq [ NO]2
[ NO ]
c. r = k[N2O2][H2] = k (keq)[NO]2[H2] = K[NO]2[H2] where K = k(keq). Reaction order = 3.
1. Equilibrium: when forward rate = reverse rate, the reaction is in equilibrium. At equilibrium, the
concentrations of reactants and products remain unchanged.
rate 1
a A + bB cC + dD rate 1 = rate 2 in equilibrium
rate 2
2. Equilibrium Constant Keq : At equilibrium, the ratio of concentration of products to the concentration of
reactants is constant, which is called equilibrium constant Keq. The expression of Keq is shown below. Liquid and
solids are not included in Keq expression, because their concentrations are constant.
c d
Equilibrium Constant keq [C ] a[ D]b concentration at equilibrium.
[ A] [ B ]
c d
Reaction Quotient Q [C ] a[ D]b use concentration at any time.
[ A] [ B ]
Difference between Keq and Q is that you must use concentrations at equilibrium for Keq, and you can use
concentration at any time for Q. Keq is constant but Q is not.
If Q < Keq, the reaction will go forward;
If Q > Keq, the reaction will go backward;
If Q = Keq, the reaction reaches equilibrium.
2. Terms
H+ H3O+ H- OH-
Hydrogen ion/proton hydronium Hydride Hydroxide
HCl, HNO3, H2SO4, H2CO3 H3PO4 H2O, HCO3-, HSO42-, H2PO4-
Monoprotic acid diprotic acid Polyprotic acid Act as both acid and base
amphiprotic or amphoteric
4. pH and pOH
1) Definition: pH = -log[H+] pOH = -log[OH-]
2) In water, pH + pOH = 14 If pH = 10, pOH = 4 Higher pH = lower [H+] = higher [OH-].
3) If pH = 7 neutral; pH < 7 acidic; pH > 7 basic
4) Example: In pure water, [H+] = 10-7 M
Q1. What is pH of pure water? A1. pH = 7
Q2. What is [OH-] ? A2. [OH-] = 10-7 M
Q3. What is pOH? A3. pOH = 7
Q4. If [H+] = 10-9 M, what is pH and pOH ? A4. pH = 9 pOH = 5
Q5. If [H ] = 10 M, is it acidic or basic?
+ -9
A5. Basic, becaus pH = 9 > 7
ka [ H ][ F ]
HF H F 7.2 104 pKa log Ka 3.1
[ HF ]
2) NH3 is a base, because if NH3 in water accepts H+ from H2O to product OH-.
kb [ NH 4 ][OH ]
NH 3 H 2O NH 4 OH 1.74 105 pKb log Kb 4.76
[ NH 3]
3) Greater Ka = stronger acid = producing more H+ at the same concentration.
Greater Kb = stronger base = produceing more OH- at the same concentration.
H N + B H H N B H
H H H H
5) Buret: a graduated glass tube filled with standard solution of acid or bases
It can measures the volume at 0.01 ml accuracy.
Rinse buret 3 times with standard solution before starting titration.
6) Indicators change colors at different pH to indicate the completion of titration.
A. Two common indicators are litmus and phenolphthalin:
Litmus red in acid and blue in base
Phenolphthalein colorless in acid and pink in base
B. Indicators themselves are weak acids. They change colors only when pH = pKa ± 1.
C. How to choose indicators: calculate pH of equivalent point then choose pKa = pH± 1.
The ranged of initial pH and final pH must include the range of color change.
7) End point: is the point indicators change color.
Equivalent point: the point reactions complete. Ideally, end point is equivalent point.
8) Titration curve: shows pH change during addition of base or acid.
Monoprotic acid HA with strong base Diprotic acids H2A with strong base.
It has one pH jump It has two pH jump
11. Buffer
1) What is Buffer: Add one drop of HCl into a cup of water, pH may change from 7 to 4;
Add one drop of HCl into a cup of buffer, pH may change from 7 to 6.9.
Buffer is a solution resisting the change of pH.
2) How to make Buffer: Mix weak acid and its conjugate base in about 1:1 ratio, you get a buffer.
Example: 0.5 M CH3COOH + 0.5 M CH3COONa this is a buffer
0.2 M NH4Cl + 0.2 M NH3 this is a buffer.
[ B]
3) What is buffer pH: pH pKa log
[ HB ]
Example 1. What is the pH of 0.5 M CH3COOH / 0.5 M CH3COONa? pKa of CH3COOH = 4.74
[0.5]
pH 4.74 log 4.74
[0.5]
Example 2. What is the pH of 0.2 M NH3 / 0.2 M NH4Cl pKb of NH3 = 4.76
[0.2]
Find pKa first: pKa = 14 - pKb = 9.24 pH 9.24 log 9.24
[0.2]
Example 3. What is the pH of 0.5 M H2CO3 / 0.6 M NaHCO4 pKa of H2CO3 = 6.37
[0.6]
pH 6.37 log 6.45
[0.5]
Example 4. If 0.4 mL of 0.5 M NaOH was added to a mixture of 50 mL of 0.5 M H2CO3 and 50 mL of 0.6 M
NaHCO4, what is the pH after adding NaOH?
When NaOH was added, [base] will increase and [acid] will decrease.
[ 50×0.6 + 0.4 0.5 ]
pH 6.37 log 100 6.46 pH increased by only 0.01.
[ 50×0.5 - 0.4 0.5 ]
100
12. Calculation of pH
1) Strong acid [H+] = C C = concentration of acid
2) Strong base [OH-] = C
3) Weak acid [ H ] Ka.C Ka = acid dissociation constant
4) Weak base [OH ] Kb.C Ka = base dissociation constant
[ B]
5) Buffer pH pKa log pKa log Ka
[ HB ]
6) Diprotic acid H2CO3 = H+ + HCO3- Ka1 = 4.27 x 10-7
HCO3- = H+ + CO3-2 Ka2 = 5.62 x 10-11
10) Salt of weak acid and weak base: Fine pH of 0.5M CH3COONH4 H
Ka.Kw
Kb
3. Oxidation numbers: number of electrons gained or losed when atoms form molecules
1) Oxidation number of elements is zero. Oxidation number of F in F2 = 0.
2) In A-B, the atom with greater electronegativity is negative. Electronegativity: F > O > N > C > H > Na
3) H is +1 with nonmetal, such as in HF, H2O, NH3. H is -1 with metal, such as in NaH, KH.
4) O is -2 in most compounds. O is -1 in H2O2, NaO2; O is +2 in F2O.
5) F is -1 in all compounds. Cl, Br and I could be -1, +1, +3, +5, +7. Cl is +7 in HClO4.
7) Group 1 is +1, Group 2 is +2. Al is +3.
8) Sum of oxidation numbers is zero for neutral molecules for equals charge of ions.
2) Reduction potential Eo represent the ability to gain electrons. From the table below, you can see that, Li+
(Eo = -3.04 V) has the lowest ability to gain an electron or Li has the highest ability to donate an electron. F2 (Eo =
+2.87) has the highest ability to gain electrons. Eo of 2H+/H2 is set to zero arbitrarily.
If you place a bulb between the conductor in the position of voltmeter, the
Bulb glows! What happened? Electrons flow through the bulb from
Zn to Cu2+. The bridge is called salt bridge. The conductor is for electrons to flow and the salt bridge is for ions
to flow to equalize the charge on two containers. What direction do the ions flow? If electrons flow to right side,
there will be too many negative charge on right side, so negative ions will flow to left side through the salt bridge.
Synonyms: Battery = Voltaic Cell = Galvanic Cell = Electrochemical Cell = Chemical Cell = Cell
E 0cell = E red
o
- E oox = E oCu 2+ /Cu - E oZn 2+ /Zn = 0.34 - (-0.76) = 1.10 V
o RT [products]
Nernst Equation: E = E - lnQ = E o - 0.059 log Q Q= R = 8.31 J/mol.k T = Kelvin
nF n [reactants]
n = number of moles of electrons F = Faraday = 96500 coulomb = charge of 1 mole electrons
Q1. What is the reduction potential of half reaction Cu2+ + 2e- = Cu at [Cu2+] = 0.1 M, T = 30 oC ?
o RT [Cu]
lnQ = E o - RT ln
(8.31)(303)
A1. E = E - = 0.34 - ln 1 0.31V [Cu] = [solid] = 1
nF nF [Cu ] 2+
(2)(96500) [0.1]
Q2. what is the cell voltage of Zn + Cu2+ = Zn2+ + Cu when [Cu2+] = 0.1 M, [Zn2+] = 2.0 M, T = 30 oC ?
[Zn 2+ ] (8.31)(303)
A2: V = V o RT
- lnQ = V o RT
- ln = 1.10 - ln 2 1.06 V
nF nF [Cu ] 2+
(2)(96500) 0.1
It It
12. Current and Mole MM gram mole of e Al+3 + 3e- = Al n = 3
96500 n 96500
Q1. Electrolysis of NaCl at current I = 5A for 2 hours. How many moles of Cl2 were produced?
It (5A)(7200s)
A1. mole of Cl2 = = = 0.19
Fn (96500)(2)
Q2. Electroplating of a Fe spoon with gold at 10A for 2 min. How many grams of gold was plated on the spoon ?
A2. Gram of Au =
I t molar mass = (10A)(120s) (197) = 2.45 g
nF (1)(96500)
Cell
Diagram
2) If a reaction potential (or a cell voltage) Eo is positive, the reaction is spontaneous or the reaction could occur.
If E is negative, it is nonspontaneous or the reaction cannot occur. If E is zero, the reaction is in equilibrium.
17. Redox Reactions: The following reactions can be used to practice balancing.
1) H2S + 2HNO3 → 2NO2 + S + 2 H2O
2) S + 2HNO3 → 2NO + H2SO4
3) Sn + 4HNO3 → SnO2 + 4NO2 + 2H2O
4) 4H+ + FeS + 3NO3- → 3NO + SO42- + Fe3+ + 2H2O
5) 5HNO3 + P → H3PO4 + 5NO2 + H2O
6) 4Zn(s) + 10H+ + NO3- 4Zn2+ + NH4+ + 3H2O
7) 2KMnO4 + 16HCl = 2MnCl2 + 5Cl2 + 2KCl + 8H2O
8) 2KMnO4 + 5K2C2O4 + 16HCl = 2MnCl2 + 10CO2 + 8H2O
9) 2KMnO4 + 3K2C2O4 + 4H2O = 2MnO2 + 6CO2 + 8KOH
10) 2MnO4- + 5H2O2 + 6 H+ → 2 Mn2+ + 5O2 + 8H2O
11) MnO2 + 4HCl = MnCl2 + Cl2 + 2H2O
12) MnO2 + 2FeSO4 + 2H2SO4 → MnSO4 + Fe2(SO4)3 + 2H2O
13) K2Cr2O7 + 14HCl = 2CrCl3 + 3Cl2 + 2KCl + 7H2O
14) K2Cr2O7 + 6FeSO4 + 7H2SO4 = Cr2(SO4)3 + 3Fe2(SO4)3 + K2SO4 + 7H2O
15) 3PbO2 + 2H2MnO3 + 6HNO3 → 3Pb(NO3)2 + 2HMnO4 + 4H2O
16) 3H2SO4 + 6FeSO4 + KClO3 3Fe2(SO4)3+ KCl + 3H2O
17) Cr2O72- + 6I- + 14H+ = 2Cr3+ + 3I2 + 7H2O
18) 2S2O32- + I2 = S4O6-2 + 2I- Iodometry
19) H2S + I2 = S + 2HI
20) 6KI + HClO3 + 5HCl = 3I2 + 3H2O + 6KCl
Chapter 13 Thermodynamics
1. Thermodynamics studies the relationship between energy, heat, work, chemical and physical changes.
System absorb heat : Q is positive heat total energy work first law
System do work on surrounding: W is positive
Q heat
3. How to calculate work ( W) U internal energy
1) If pressure is constant: W = PV = P(Vf - Vi) W work
Vf
nRT dV = nRT ln Vf
Vf J unit for Q, U, W
2) If idea gas at constant T: W= Vi PdV
Vi V Vi R 8.31 J/mol.K
1 1 - P2 V2
PV nR (T1-T2 ) Cp 5 T Kelvin
3) If idea gas at adiabatic (Q = 0) : W r -1
r -1
r=
Cv 3 m mass
C heat of capacity
4. How to calculate internal energy ( U)
Cv 3R
idea gas
3 2
1) For idea gas : U RT per mole
2 Cp 5R
idea gas
2) For idea gas : U = m Cv T 2
5. How to calculate heat ( Q ) Q = m C T or Q = m Hvap Cv 5R
diatomic gas
2
Cp 7R
6. Entropy (S) and Change of Entropy (S) 2
diatomic gas
12. Calculate S
Qrev Q max Definition of entropy Wmax Vf V change at constant T
S S nRTln for idea gas
T T T Vi
1. Nuclear Chemistry study the change of nuclei. Can nuclei change? Yes. Why?
2. Stability of Nuclei
Nuclei contain protons and neutrons. Some nuclei are stable and some are not stable. Here is the reason. Protons
have positive charge and neutrons have no charge. Like charges repel each other. Wait, if protons repel each other,
how can they stay together to form nuclei? There must be another force to bind them. The force binding protons
and neutrons to form nuclei is called strong nuclear force. If the strong force is greater than the repel force of
protons, the nucleus is stable. Otherwise, it is not stable.
3) If a nucleus has less mass than its atomic mass, it has too less neutrons. Then it emits positron (positive
electron) for proton to change to neutron. This is positron decay .
1
1 p 10 e 01n 37
19 K 10 e 18
37
Ar
4) Gamma decay: excited nucleus ground state nucleus + 0
0
(gamma ray - high energy photon)
5) Electron capture:
201
80 Hg + 0
1 e 201
79 Au + 00
4. Radioactivity: Unstable nuclei keep emitting particles as stated above. This phenomenon is radioactivity.
Types of Radioactive decay Penetrating ability of particles
7. Detection of radioactivity
When radioactive nuclei emit particles, we can use some devices to detect them.
1) Photographic plate: based on AgBr + hv = Ag + Br (X-ray plate is an example)
2) Geiger counter: based on ionization caused by emitted particles.
3) Scintillation counter: based on phosphorescence produced by emitted particles.
Half-Life (T1/2): the time required for half nuclei to decay. Half-life of Au-198 is 3 days.
2) Nuclear reactor is a device using nuclear fission to produce heat in nuclear power plants. The heat is used to
produce electricity by a steam turbine and an electric generator. Because the rate of fission increase exponentially,
it is controlled by control rods and moderators.
Control rods absorb neutrons to decrease the rate of fission. Control rods are composed of elements such as Cd,
B, In and Ag, all of which absorb neutrons.
Moderators slow neutrons to turn fast neutrons into slow neutrons to sustain fission chain reactions. Common
moderators include H2O, graphite, D2O (heavy water).
3) Nuclear fusion: Two nuclei combine into one nucleus. Fusion is initiated by very high temperature (10
million oC) and produces huge amount of energy. Hydrogen bomb and nuclear reaction in the Sun are two
examples.
Fusion 4 11H 24 He 2 10 e energy reaction in the Sun
4) Einstein equation E = mC 2
In a nuclear reaction, some mass converts into energy.
10. Polymers:
1) Polymer: a large molecule containing many repeated units.
2) Monomer: a small molecule used to synthesize a polymer. It is the repeated unit of a polymer.
3) Examples
Monomer Polymer Natural or Synthetic
Amino acids Protein natural
Nucleotides = deoxyribose, 4 bases, phosphate DNA natural
Nucleotides = ribose, 4 bases, phosphate RNA natural
α-glucose Starch natural
β -glucose Cellulose natural
α-glucose more branches Glucogen natural
CH2=CH2, CHCl=CHCl Plastic - PVC Synthetic
Rubber Synthetic
=
C C
C6H6 C C
H C H
H
Just know it. But charge x 2 can give a good guess. Ag1+ 1 2
Zn2+ 2 4
Fe3+ 3 6
6. Valence bond theory ( See examples in the first page of this chapter)
1) Ligands donate electron pairs to metal ions to form coordinate bonds.
2) Metal orbitals are hybridized to form bonds, which determine geometries.
Number of 2 3 4 5 6
ligands
Hybrid orbital sp sp2 sp3 (d10) dsp2 (d8) sp3d sp3d2
Linear Trigonal planar Tetrahedron Square planar Trigonal bipyramidal Octahedron
Geometry
1) Energy Splitting
A. Octahedron field: Two energy levels with oct
B. Tetrahedron field: Two energy levels with tet = 4/9 of oct
C. Square planar: Four four energy levels
If ligands are CN- and CO, complexes are more likely to be low spin. This explains paramagnetic or diamagnetic
properties.
CoF63- Co(NH3)63+
hexafluorochromium (III) ion hexaamminechromium (III) ion
3. Separation funnel Separate two insoluble liquids. Water (top) /chloroform CHCl3 (bottom)
6. Electrophoresis Separate ions with different charges under electric field such as proteins with different
PI or DNA
7. Centrifugation Separate small particles in liquid by rapid rotation, such as blood cells from plasma
3. Acid and Base Titration (see chapter of acids and bases also)
1) Three devices for measuring liquid at 0.01 ml accuracy: buret, volumetric flask, volumetric pipette.
2) Rinse buret with standard solution 3 times before titration.
Don’t rinse the beaker to hold acid or base to be titrated.
3) Titration curve of monoprotic and diprotic acids titrated by strong base.
Monoprotic Diprotic
A
Io I I
light solution log o = A (absorbance)
I 0.48
I
I < Io = T (transmittance)
Io
6. H2O: sp3, two electron pair, bent, polar solvent, hydrogen bonding, pH = 7
1) Polar dissolve polar. H2O can dissolve polar molecules such as sugar, NaCl, proteins.
3) React with group 1 and 2 to produce H2 and base such as NaOH, Ca(OH)2
7. NH3: sp3, one electron pair, trigonal pymidal, polar, weak base, hydrogen bonding
1) Reaction as a base: NH3 + HCl = NH4Cl
3) Reaction as Lewis base: NH3 + BF3 = NH3BF3
8. Solubility
Always soluble Precipitates
Positive ion Na , K ,
+ +
NH4+ and group 1 cations. AgCl BaSO4 CaCO3 Fe(OH)3 FeS black
Negative ion - -
NO3 , CH3COO , HCO3 , ClO3 , ClO4 - - - PbCl2 CaSO4 Ca3(PO4)2 Al(OH)3 CuS black
Hg2Cl2 PbSO4 PbI2 yellow ZnS white HgS black
Copy right by Dr. Sun WeChat: DrSunNewYork 69
Dr. Sun Chemistry Summary .
10. Color You need to remember the following colors for SAT and AP
You just need to know that transition metal ions are colorful. (Zn2+ has no color)
1. Units
Pressure Length Volume Gas constant Electric charge
1 atm = 760 mmHg mm = 10 m-3
Liter = 1000 mL R = 0.082 atm.L/mol.K Faraday = 96500 Coulomb
= 760 torr nm = 10-9 m m3 = 1000 L = 8.31 J/mol.K e = 1.6 x 10-19 Coulomb
= 101.3 kPa pm = 10-12 m
Temperature Energy/work Mole Mass
K = C + 273
o
calorie = 4.18 Joule 1 mole = 6.02 x 1023
gram = 6.02x1023 amu
1 mole O2 = 32 g Kg = 1000 gram
2. Conversion Factors
7 day 24 h 3600 s
A. how many seconds in 8 weeks? 8 week 4838400 s 3 conversion factors
week day h
6.02 x1023 molecule 3.01x1023 molecules
B. how many molecules in 9g water? 9 g mole
18 g mole
2 conversion factors
4. Overview of Chemistry
synthesis
proton
atoms bonding molecules decomposition
neutron reactions single replacement
element compound
electron double relacement
acid-base reaction
intermolecular force
solid stoichiometry
nuclear change liquid
mole redox reaction
gas
phase change
Dr. Sun solution
organic reaction
Chemistry is well organized central science. You should be able to study more advanced chemistry after
understanding this summary. Good luck in your chemistry SAT and AP tests ! Feel free to write me at
gsun98@yahoo.com if you have any suggestions. Dr. Sun in New York 2019.