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o
DS is positive
o
DS is negative
Chemical Kinetics
D
2 N 2O5 ( g )
4 NO2 ( g ) O 2 ( g )
D
2 N 2O5 ( g )
4 NO2 ( g ) O 2 ( g )
𝑟 𝛼 [𝑁2 𝑂5 ] 𝑚
𝑟 = −𝑘 [𝑁2 𝑂5 ]𝑚
Rate Equation (Rate Law)
For a reaction Aproducts we write the
equation: rate = k[A]n
This is called the rate equation (or rate law)
The exponent n is the order of the
reaction
If n=1, first order
If n=2, second order
n must be determined experimentally
This exponent is not the same as the coefficient
of the reactant in the balanced equation
Rate Equation
A + B products
rate = k[A]n[B]m
CH4+2O2CO2+2H2O
Rate = k[CH4]n[O2]m
Equilibrium
Rate and Reversibility of Reactions
Equilibrium reactions – chemical reactions that do not
go to completion
Completion – all reactants have been converted to
products
Equilibrium reactions are also called Incomplete
reactions
Seen with both physical and chemical processes
After no further observable change, measurable
quantities of reactants and products remain the same
Chemical Equilibrium Expression: Ammonia Synthesis
kf [NH3 ]p
K eq n m
kr [N 2 ] [H 2 ]
• The exponents in the rate expression are numerically
equal to the coefficients
[NH3 ]2
K eq
[N 2 ][ H 2 ]3
• Keq is a constant at constant temperature
Writing Equilibrium-Constant Expressions
Equilibrium constant expressions can only be
written after a correct, balanced chemical
equation
Each chemical reaction has a unique
equilibrium constant value at a specified
temperature
Writing Equilibrium-Constant Expressions
1. Changes in concentration
2. Changes in pressure/volume
3. Changes in temperature
4. Presence of catalyst
Le Chatelier’s Principle
State of equilibrium
Stress is applied
System adjust to
relieve the stress
Attain state of
equilibrium
Effect of Concentration
Adding or removing either reactants or
products at a fixed volume is saying that the
concentration is changed
Removing material decreases concentration
System will react to this stress to return
concentrations to the appropriate ratio
A: Reaction at equilibrium
B: Shift to reactant with
more red color
C: Shift to product with loss
of red color
A B C
Effect of Concentration
Legend:
Orange solution (equilibrium)
Red solution (reactant)
Yellow solution (product)
Effect of Heat: Addition of heat is treated
as increasing the amount of product
H H
C C
HC CH HC CH
HC CH HC CH
C C
H H
Benzene Structure – Modern
Cl
NO2
CH2 CH3
chlorobenzene
nitrobenzene
ethylbenzene
Substituted Benzenes: o,p,m
CH2 CH3
Br CH3
1-bromo-2-ethylbenzene
o-bromoethylbenzene NO2
3-nitrotoluene
m-nitrotoluene
Cl Cl
1,4-dichlorobenzene
p-dichlorobenzene
Historical Nomenclature of Substituted
Benzene
CH3
OH
NH2
COOH
Toluene
Phenol
Aniline
Benzoic
acid
Benzene As a Substituent
When the benzene ring is a substituent
on a chain (C6H5), it is called a phenyl
group
CH2 CH CH2
CH CH3
4-phenyl-1-pentene
Polynuclear Aromatic Hydrocarbons (PAH)
Alcohols (ROH)
CH3
CH3 C CH3 CH3CH CH3
OH OH
t-butyl alcohol isopropyl alcohol
Phenol (Ar-OH)
Ethers (ROR)
CH3 CH2O CH2 CH3
Diethyl ether -
First successful
general anesthetic
F Cl
CH3O C C H Penthrane
F Cl
12.9 Thiols
THIOLS (R-SH)
CH3
CH3 CH CH2 CH2
SH
3-methy-1-butanethiol
Disulfide Formation: disulfide bridge
Carbohydrates
Carbohydrate : CnH2nOn, where n varies from 3 to 8
a polyhydroxyaldehyde or polyhydroxyketone, or a
substance that gives these compounds on hydrolysis
Monosaccharide
a carbohydrate that cannot be hydrolyzed to a simpler carbohydrate
O
Glycerol
CH2O C R1
part O Fatty acid
CH O C R2 chains
O
CH2O C R3
Fats and Oils
Triglycerides or triacylglycerols
Fats are a combination of glycerol and the
fatty acids
Fats mainly come from animals, unless
from fish, and are solid at room
temperature
Oils mainly come from plants, and are
liquid at room temperature
Phosphoglycerides
Phospholipid is a more
general term
Any lipid containing G
phosphorus l Fatty Acid
Phosphoglycerides contain: y
c
Fatty Acid
Glycerol e
r
Fatty acid o
Phosphoric Acid
l
Phosphoric acid with an
amino alcohol
Alcohol
Replace an end fatty acid of
a triglyceride with a
phosphoric acid linked to an
amino alcohol
Nonglyceride Lipids
Sphingolipids
These lipids are based on sphingosine
o Long-chain
o Nitrogen-containing
o Alcohol
Amphipathic, like phospholipids
o Polar head group
o Two nonpolar fatty acid tail
Structural component of cellular membranes
Major categories
o Sphingomyelins
o Glycosphingolipids
Major categories
o Sphingomyelins
o Glycosphingolipids
Types of Sphingolipids
Sphingomyelins
Glycosphingolipids
Types of Sphingolipids
Sphingomyelins
Structural lipid of nerve cell membranes
Myelin sheath feature
Glycosphingolipids: Built on a ceramide
Types of Sphingolipids
Glycosphingolipids
Cerebrosides have a single monosaccharide
head group
Glucocerebroside
Galactocerebroside
Structure Taken from:
http://www.suite101.com/view_image.cfm/230204
Structure of a nucleotide
Nitrogenous Bases
Taken from: http://hyperphysics.phy-astr.gsu.edu/Hbase/organic/base.html
Numbering Nitrogenous Bases
Uracil
Thymine
Cystosine
Pyrimidine
b-D-ribofuranose found in RNA
Adenine-Thymine
The Central Dogma of Molecular Biology
figure taken from : http://www.accessexcellence.org/RC/VL/GG/central.php
Nuclear Chemistry
Nuclear Chemistry
mass number
11
(number of protons
and neutrons)
5 B
atomic number
(number of protons)
ISOTOPES, ISOBARS, ISOTONES
11 12 13
5 B 5 B 5 B
31 31 31
14 X 15 X 16 X
26 27 28
12 M 13 M 14 M
Properties of Alpha, Beta, and
Gamma Radiation
Ionizing radiation – produces a trail of ions
throughout the material that it penetrates
The penetrating power of the radiation
determines the ionizing damage that
can be caused
• Alpha particle < beta particle < gamma rays
Types of Radioactive Decay: Balancing Nuclear Equations
Beta decay - ejection of a b particle from the nucleus from the conversion
of a neutron into a proton and the expulsion of 0-1b. The product nuclide
will have the same Z but will be one atomic number higher.
2
4
2 He 4
2 He α 4
2 α
Beta Particles and Positrons
Beta particles (b) – fast-moving electron
• Emitted from the nucleus as a
neutron is converted to a proton
• Higher speed particles, more
penetrating than alpha particles
• The symbol is…
0
1 e 0
-1 β β
Beta Decay
Upon decomposition, nitrogen-16 produces
oxygen-16 and a beta particle
16
7 N O e 16
8
0
-1
Positron Emission
A positron has same mass as an electron, or beta
particle, BUT opposite charge (+)
the product nuclide has the same mass number as the
parent BUT the atomic number has decreased by one
11
6 C 11
5 B 0
1 e
11
6 C 11
5 B b 0
1
Gamma Rays
Gamma Rays () – pure energy
(electromagnetic radiation)
Highly energetic
The most penetrating form of radiation
Symbol is simply…
Gamma Production
Gamma radiation occurs to increase the
stability of an isotope
The atomic mass and number do not change
Usually gamma rays are emitted along with
alpha or beta particles
99m
43 Tc Tc 99
43
Writing a Balanced Nuclear Equation
238 = 234 + 4
mass number
92 = 90 + 2
atomic number
Balancing Equations for Nuclear Reactions
A = 36 and Z = 16 36 + 0-1e 36
17Cl 16S
Nuclear Stability and Mode of Decay
•Very few stable nuclides exist with N/Z < 1.
•Well over half the stable nuclides have both even N and even Z.
2
1 H H He
3
1
4
2
1
0 n energy
Radiation Exposure and Safety
Time of Exposure
Effects are cumulative
Waste Disposal
disposal sites are considered temporary
Decay rate (A) = DN/Dt
curie (Ci) =
number of nuclei disintegrating each second in 1g of radium-226 =
3.70x1010d/s
The Roentgen
The amount of radiation needed to produce 2 x 109 ion
pairs when passing through one cm3 of air at 0oC
Used for very high energy ionizing radiation only
Units of Radiation Measurement