Lecture 1

01/29/2015

Why is it important to separate physical and kinetic parameters?

a. This is important because physical properties do not dictate rate
equation however the molecular process does
Depending on the rate of reaction determines the vessel in which the
mass transfer will occur in
Laminate flow in a reaction vessel means that it does not have complete
mixing in the mixing region
a. What kind of shape prevents laminate flow?
o Fluted shape helps prevent laminate flow
Turbulent zone has complete mixing
Type of mode operation: (you also have stir tank and tube reactor)
a. Batch
o In a tube vessel the system is put on a loop mode to entail
mixing
o Batch reactors are often use in small scale productions and
when operating conditions are flexible
o Not run in steady state and does not have constant rate
b. Continuous
o In a tube vessel the system is continuously injecting reactants
and removing products
o Continuous is used for large scale production
o Run in steady state
Homogenous gas phase reactions take place in a tube reactor and this is
done so because it is at high pressure and temperature. This is difficult to
do in a batch reactor because it is difficult to seal a stir tank
Lid-phase and liquid-solid-phase heterogeneous reactions can be done in
either tube or stir tank batch
aA+bB xX+zZ
1 dN X 1 dN Z 1 dN A 1 dN B
=
=
=
a. r x =
x V dt z V dt a V dt b V dt
b. This equation is used and not concentration because the volume
can change and is not constant due to expansion and can condense
under pressure.
[Insert graphs] Average rate takes the average between two points for
the rate, which this is not used often.
[Insert graph] Instantaneous rate is a rate at a signal point in time

[Insert graph] Initial rate is when the rate is taken at t=0. This is done in
equilibrium reactions because the rate is affected by the consumption and
production of reactants and products. So this is valuable to determine the
rate before any products are produced
[Insert graph] Tangent=instantaneous rate a specific point. Shows the
dependence of rate on [M]
Empirical rate equations
a. aA+bB Products

b. r=k [ A ] [ B ]
c. rate constant (k) is a constant and does not depend on the
concentration of the reactants but is only a constant if temperature,
pressure, and [catalyst] do not change
d. also and are independent of [M] and time
A+2B 3Z
a. For every molecule of A consumed 2 molecules of B are consumed

b. r a=k a [ A ] [ B ]
1
1
c. k =k A = k B= k Z
2
3
In order to determine the order of a reaction you need to plot the rate of
change vs [A] and which ever predicted order gives you a linear relations
then that is your order.
1st order
a. r=k[A]
nd
2 order
2
a. r=k [ A ]
b. or r=k[A][B]
Elementary, composite, and chain reactions
a. Elementary: the reaction occurs in a single step. The products are
formed from the reactants
b. Molecularity of an elementary reaction = # of reactant particles in
each step
c. Composite: more than one elementary reaction
d. Chain reaction: includes a cycle of reactions in the composite
scheme
o Initiation step: generates the reactive species mostly a free
radical
o Chain propagation: one of the initiation species will react and
form a product and a reacting species. Any step that
generates a product and a reacting species
o Termination: the reacting species is removed from the
reaction medium

Catalyst and inhibition

Catalyst: is both a reactant and product because it is not consumed. It
increases the rate of reaction by lowering the activation energy.
a. The catalyst does not appear in the rate equation. However, the
rate will change with a change in catalyst concentration
Inhibition: diminishes rate and is often consumed in the reaction.
r with I
a. Deg. of Inhibition=1
r w /o I
Analysis of Kinetic Results
Differential method: comparison of predicted and observed rates by
differentiating the experimental data
a. Best if you know nothing about the reaction
Integration method: comparison of the predicted and observed
compositions of the reaction mixture as a function of time
a. Good if order is known and if you want to calculate an accurate
value of k because if you have a fractional order it can disguise it
Difference between differential and integration method: The rate constant
(k) is determined by either extrapolating or taking an average in some
cases for the differential method.

Zero- order
d [ A ]
0
=k [ A ] =k
a. R=
dt
b. [ A ] t= [ A ]o kt
[ A ]o
c. t 1 =
2k r
2

First order
kt
a. [ A ] t= [ A ]o e
[ A ]t
=kt
b. ln
[ A ]o

( )

Second order
1 d [ A ]
2
=k [ A ]
a. r=
2 dt
1
1
=
+ kt
b.
[ A ]t [ A ] o
d [ A ]
=k [ A ][ B ]
c. r=
dt
[ A ] o ( [ B ]ox )
1
ln
=kt
d.
[ B ] o [ A ]o [ B ]o ( [ A ]ox )

e.
f.

d [ A ]
=k [ A ][ B ]
dt
[ A ]o ( [ B ] o2 x )
1
ln
=kt
[ B ] o2 [ A ] o
[ B ] o ( [ A ] ox )

A +2 B P ,

r=

Third order
a. A+A+A P
1
1
= 2 6 kt
b.
2
[ A ] [ A ]o
c. 2 A+ B C

[ A]

( ox [ B ] o )
[ A ] o ( [ B ]o 2 x )

d.

2x
1
+
ln
( 2 [ A ]o [ B ]o ) ( [ B ] o2 x ) [ B ] o ( 2 [ A ] o[ B ] o )2
k A t=

f.

A + B+C P
3
t1 =
2 k a b o co
2

g.

bo ( a ox )
1
ln
2 aobo
ao ( b o2 x )

e.

nth order
a.
b.

dx
=k ( aox )n
dt
1
1
1
kt=
n1
n1
n1 ( a ox )
ao
r=

n1

c.

t1 =
2

(2 1)
k A ( n1 ) ano1

Isolation method
a. If you have a reactant in excess (ie: [B]>>[A]) then you can treat
the reactant that is excess as a constant (k=k[B]) and your rate
will depend on the concentration of the other reactant.

Half life t1/2

a. The time it takes for the [M]i to reach half.
b. Also t1/2=1/k

( )
k1
AZ
k 1

Equilibrium rxn

both the forward and reverse rxn are first

x e =[ Z ] at equilibrium ,
order,
concentration
of
Z=x
at
t
and
dx
=k 1 ( aox ) k 1 x the ( a ox ) is the consumption and the formation is
dt
dx
dx k 1 a o
k1 x
=0=k 1 ( aox e )k1 x e . Then
=
(x e x)
the
and
or
dt
dt
xe
k 1
xe
m
dx x e
= ln
[Z] k1
intergration
.
Remember
also xe is
K eq = n =
dt a o
x e x

[ A]

( )

obtained when the [M] does not change over time.

Arrehenius equation
a. Shows the dependency of k on temperature for an elementary
process. A= the prexponetial factor does not change with
temperature it is a constant
b.

Ea

k =A e RT
Two parameter Temp Dependency Eq.
a. This shows how the pre-expontetial factor is temp dependency you
know when it is temp dependent if you do not have a linear graph
b.
c.

Eo
RT

k =( A T ) e
Ea =Eo +mRT

Lecture 2

Experimental Procedures for kinetic studies

a. Identify the product and intermediates
b. Determine the concentration of all the present species
c. Determine what method to use in order to follow the rate of
reaction
d. Kinetic analysis
e. Determine the mechanism
Instruments that can be used in order to determine the concentration or
to identify the compound are:
a. Chromatography
o Separates compounds in a sample based on how they interact
with a stationary phase and a moving phase
o Can detect small amounts of species up to 1010 moles or less
o Is used as quantification method cannot be used to identify a
compound
o Need to prepare a calibration curve for each species (area vs
[M])
b. Mass spectrometry
o Sample is vaporized and is bombarded with electrons so that te
molecules are ionized. Once ionized the detector measures the
mass/charge ratio and based on this the molecular weight is
determined and you can identify you compound.
o Can detect up to 1012 moles
o Quick analysis time ~ 105 s
o If you have a sample with multiple species it needs to b
separated first by chromatography
o The ionization chamber: The sample is introduce into the
chamber and is bombarded with electrons that are produce by a
filament. Once ionized the species are accelerated through by
plates that are (-) charged, which have increasing potential
difference. If a charge is not ionized or has a (-) charge it will be
removed by the plates
o The energy required to remove an electron from an atom o
molecule is its ionization potential
o Quadruple mass analyzer utilizes 4 charged poles and will only
allow certain m/z to go through, which it can select which m/z
based on the magnetic field
o Most abundant peak formed is the base peak whereas the
molecular ion is the molecular weight
c. Spectroscopy
o Three features of importance to the kinecticist are:

a. The frequency and the fine structure of the lines give the
identity of the molecules. The lines will help identify the
structure
b. The intensity of the lines give the concentration
c. The width of line enables kinetic features of the transition
and the excited state to be determine. The line widths
gives us information of the lifetime o the intermediates or
of the molecule
o Spectra can be generated by either absorption or emission
o Spectra can be generated in several different regions of the
electromagnetic spectrum (the smaller the the higher the
energy). VIP DOF=3N, atoms have at least 3 translational
movements, ie He has only 3 translational. DOF: where a
molecule can put its energy
a. Microwave region: deals with rotational spectroscopy,
which utilizes photons in the microwave region to cause
transitions between the rotational energy levels of a gas
molecule. Has to be a gas because the intramolecular
interactions hinder the rotations in liquid and solid form.
Molecules are able to rotate on a fixed orthogonal axis an
rotation about each unique axis is associated with a set of
quantized (energy that is the smallest bit of
electromagnetic radiation that can be emitted) energy
levels.
b. Infrared region: Deals with wavelengths that are longer
but shorter then the visible region and mainly deals with
absorption. The graph is absorbance vs wavelength. The
sample can be solid, liquid, or gaseous however cannot
have water because it will absorb the wavelength. You can
experience vibrations in the near-IR with higher energy or
in the mid-IR you can have rotational-vibrational structure
or in the far-IR you can have rotational because it is on the
lower energy. Utilizes the fact that molecules absorb
specific frequencies that are characteristics to their
structure. In order to experience a vibrational mode in IR it
needs to have a change in dipole, for linear molecules the
degree of freedom is 3N-5 and for a non-linear system 3N6. However, simple diatomic molecules have only one bond
and only one vibrational band, ie N2, and the band is not
observed in the IR spectrum but is in the Raman spectrum.
Asymmetrical diatomic molecules, ie CO, absorb in IR.

c. Raman Spectroscopy: A technique used to observe

vibrational, rotational, and other low frequency modes in a
system. It relies on inelastic scattering of monochromatic
light (ie a laser). The laser interacts with the molecular
vibrations and will cause a shift in the lasers photons. The
shift in energy gives information about the vibrational
modes. It studies vibrational frequencies with a laser. Can
be solid, liquid, or gas phase. The molecule will absorb the
electromagnetic radiation and will interact with the
polarizable electron density and the bonds of the molecule.
Qualitative.
d. Visible spectroscopy and Ultraviolet: refers to absorption
spectroscopy in the ultraviolet or visible region. It uses
light in the visible or near-IR region. The incident light is
absorbed by the sample and the light that reaches the
detector has been decreased because a portion of the
light has been absorbed. This deals with electronic
transitions, ie you can look at the d-orbital of a ligand.
Molecules contained pi or non-bonding electrons can
absorb energy in the form of Uv or Visible light to excite
these electrons to a higher anti-bonding molecular orbital.
The more readily the electron is excited the longer the
wavelength of light it can absorb because the longer the
wavelength the lower the energy. A quantitative method.
e. X-ray: When an electron from the inner shell of an atom is
excited by the energy of a photon, it moves to a higher
energy level (an outer shell). The difference in energy is
emitted as a photon which has a wavelength that is
characteristic for that element. This is used as a qualitative
method.

o XPS: x-ray photoelectron spectroscopy. Purpose is

used to give information about inorganic and organic
oxidation states and what it is bound to. The
equation that is used to determine the binding
energy (BE) is as followed: hv=BE+KE. You measure
the hv (which is the photon used to excite the
electron) by using a beam of x-rays while measuring
the kinetic energy (KE) and the number of escaped
electrons from the material. The binding energy (BE
and aka ionization energy) of an atom or molecules
describes the minimum amount of energy required to
remove an electron from the atom or molecule,
which the BE identifies the element and its state and
is a function of the oxidation state and what is bound
to the atom. Oxidation state: is a number assigned
to a compound inorder to help us describe redox
reactions.
Beers law is used to determine the concentration of a species:
I
A=log
=eCl
I0
o Fluorescence: intensity=f [reactant] or
ln ( intensity )=ln ( f )+ ln ( reactant )
Lasers in kinetic studies:
o Short time pulses: used to gather information over the fastest
technique possible can be as fast as a femento second
o High energy pulses: gives good string signal for even the most
dilute samples. This can put high energy to increase the S/N.
o Very narrow frequency, which results in excellent resolution
o Small area focused beam
Intersystem and internal crossing:
o Intersystem: a crossover between states of different multiplicity
o Internal: a crossover between states of the same multiplicity
Population inversion occurs when a system, such as atoms or molecules,
exist in a state with more members in the excited state than in the lower
energy states. This is very important with lasers because the production
of a population inversion is a necessary step in the working of laser.
Spin techniques (ESR and NMR)
o Electron spin resonance: is mainly used for free radicals. It is
a technique used for studying materials with unpaired
electrons. It has a similar concept to that of NMR but it
excites the electron spins not the spins of the atomic nuclei in
NMR. Different energy transitions in microwave region for the
radical atom in different environments

( )

o NMR: nuclear magnetic resonance spectroscopy: utilizes the

magnetic properties of certain atomic nuclei and you change
the magnetic field to look at the change in the magnetic gyro
ratio. It determines the physical and chemical properties of
atoms or molecules. Used with odd number nuclei (ie, H, or
C13, etc.)
Pressure changes can be used to monitor rates of reaction (pV=nRT).
However, this method can only be used for reactions that have an overall
change in moles and are in the gas phase. Also in order to follow pressure
change the volume and temperature must be held constant.