Appendix I--Short Guide to Kinetics

Consider two reactions which have the same stoichiometry:

H2 + I2 2 HI (1)

H2 + Br2 2 HBr (2)

However, if various amounts of the reactants are mixed, the rate of product formation shows a
different dependence on the reactant concentrations:

d[HI]
k H 2 I 2 (3)
dt

1/ 2
d[HBr] k H 2 Br2
(4)
dt 1 k HBr Br2

The different rate expressions [eqns (3) and (4)] or "rate laws" for reactions (1) and (2) suggest
that the detailed pathway in which bonds are made and broken, i.e., the reaction "mechanism",
differs for the two reactions. Rate law (3) is consistent with a bimolecular pathway for reaction
(1):

H I H I H I
+ +
H I H I H I

However, rate law (4) is not consistent with such a pathway for eqn (2). A more complex set of
reactions, such as the following, is indicated:

Br2 2 Br

Br + H2 HBr + H

H + Br2 HBr + Br

H + HBr H2 + Br

The goal of a kinetics study is to determine a rate law. This in turn can eliminate some possible
mechanisms, but it cannot be used to prove a mechanism. A mechanism is only a hypothesis
which fits the facts in hand. New facts may require a new mechanism.

A1
Consider the reaction A B, then if the disappearance of A is followed, a curve such as the
following will be observed:

[A]o
[A]

time
The reaction rate at any time t
is the derivative of this curve: Rate = - d[A] = d[B]
dt dt

The rate may be a simple function of [A], such as:

d[ A]
k[ A]n
dt

In order to determine if this is the case, an integrated form of such an expression is more conve-
nient:

n = o (zero order)

Rate = -d[A] = k [A] = k

dt

-d[A] = k dt or d[A] = -k dt

[A]t t
[A]o
d[A] = -ko dt
[A]t - [A]o = -kt

[A]t = [A]o - kt

[A]o
slope = -k
[A]

time

A2
n = 1 (first order) common case

-d[A] = k[A]
dt
d[A] = -k dt (separate variables)
[A]
[A]t t
d[A] = -k
[A]o [A] o
dt

ln[A]t - ln[A]o = -kt

ln[A]t = ln[A]o - kt linear plot 2

[A]o ln[A]o
slope = -k
[A] ln[A]

1 2
time time

ln [A]t /[A]o = -kt

[A]t /[A]o = e-kt exponential plot 1

A3
n = 2 (second order)

-d[A] = k[A]2
dt
-d[A] = k dt
[A]2
[A]t t

-d[A] = k dt
[A]o [A]2 o slope=k
1 1
[A]t - [A]o = kt
1
1 1 [A] 1
or [A]t = [A]o + kt [A]o
time

Definition of Half-Life

half-life t1/2 is when [A]t = 1 [A]o

2
[A]o
zero order -kt1/2 = 1 [A]o - [A]o or t1/2 = 1
2 2 k

first order -kt1/2 = ln (1/2[A]o /[A]o or t1/2 = ln 2 = 0.693

k k
NOTE: only for 1st order reactions is t1/2 independent of [A]o

second order +kt 1/2 = 1 1 - 1 or t1/2 = 1

[A]o [A]o k[A]o
2

A4
pseudo-first order

another kind of 2nd order reaction:

-d[A] = k[A][B] also: -d[A] = k[A][B][C], etc.

dt dt

1st order in each [A] and [B], 2nd order overall

usually carried out under pseudo first order conditions, i.e., [B] > 10[A]

[B] changes little and is effectively constant = Bo

-d[A] = k[A][B]o = kobs [A]

dt

pseudo 1st order

rate const.
= k[B]o

plots at slope = k
diff values
-ln[A]b of [B]o kobs

time [B]o

A5
Consider the system:

k1
A B
k-1

at equilibrium: k1 [A]eq = k-1 [B]eq

k1 [B]eq
or = = K (eq. const.)
k-1 [A]eq

in general:

d[A] = k [B] - k [A]

dt -1 1

but [A] + [B] is constant = Co

d[A] = k (C -[A]) - k [A]

-1 o 1
dt
= k-1 Co -[A](k1 +k-1 )

at equil. d[A] = O = k C - [A] (k +k )

dt -1 o eq 1 -1

d[A] = [A] (k k ) - [A](k +k )

dt eq 1 -1 1 -1

= -(k1 +k-1 )([A]-[A]eq)

-- this is an equation for 1st order approach to equilibrium with rate const. k1 + k-1

-- if K is known k1 or k-1 can be calculated.

A6
Slightly more complicated case:

k1 k3
A+B C D
k-1

"pre-equilibrium" - complex C required before formation of D

Rate = d[D] = k3 [C]t

dt formation destruction
-- what is [C]t ? d[C] = k [A][B] - k [C] - k [C]
dt 1 3 1

can't solve for [c] t alone

-- if C is a reactive intermediate, can make the "steady-state assumption", i.e., d[C] ~

dt 0

then
0 = k1 [A][B] - k3 [C] - k-1 [C]

k1 [A][B]
or [C] =
k3 +k-1

k3 k1 [A][B] k1 [A][B]
and d[D] = =
dt k3 + k-1 1 + k-1/
k3

k
(a) if k3 << k-1 , reduces to k3 K[A][B], K = k 1 C D is rate determining step
-1

(b) if [B] >> [A], treat as [B] ~ [B]o pseudo first order

A7
 Temperature Dependence of Rate Constants

(1) empirical Arrhenius equation:

activation energy Ea activation energy

1 - Ea
ln k T k = A e RT A pre-exponential or
frequency factor frequency factor

form of eqn can be derived from stat.

mech. collision theory
~10 13 sec-1 for uni-molecular
1
plot lnk vs. /T Ea, A
i.e. lnk = lnA - Ea/RT

(2) transition state theory (Eyring):

patterned after equil: X Y, K = [Y]

[X]
Standard free energy
-RT ln K = Go calc from stat. mech.
= Ho - TSo
enthalpy entropy

assume reactants in pseudo equilibrium with the transition state (also activated complex)

A8
 k1 k2
A+B C D+E Rate = k2 [C ]*

k-1 [C ]*
K = [A][B] = K k2 [A][B]

now, Rate = k[A][B] and -RT ln K = G

so k = k2 K and K = e-G /RT

kBT -G/RT
so k = e k2
kBT
h h
units s-1 kB Boltzmann const.
= 1.3805 x 10 -16 erg /K
y = mx+b Form h Planck's const.
ln (k /T) = ln ( kB /h ) - G /RT = 6.625 x 10 -27 erg.sec
log ( k B/h ) = 10.319
ln (k /T) vs 1 /T gives G
ln (k B/h ) = 23.760

A9
Eyring equation:

kBT -G/RT k T -H/RT S /R G = H - TS

k = e = Bh e e
h

enthalpy entropy
k T S /R -H/RT of of
= Bh
e e
activation activation
weakly T strongly
dep simi- T dep simi-
lar to A lar to e-Ea /RT

(NOTE) but predicted dependence of ln k on 1/T is slightly different for [different

models!] Arrhenius and Eyring equations.

k1
for system A B
k-1

G 1

free G -1
o
energy A G
(G)
B
reaction coordinate

1 bond-breaking activated H >> O, S > O

Ln M__ X [Ln MX] Ln M + X

2 bond-making activated H 10 kcal , S << O

mole
X
Ln M__ X + L' [L n ML' ] L n-1 M (L')X + L

A10
 Appendix II--Short Guide to Electrochemistry
See also the published article related to these notes: L. R. Faulkner, J. Chem. Educ., 1983, 60, 262.

Basic Electrochemical Concepts

It is useful to think about an electrode as a reagent with tunable reducing and oxidizing power. The
potential of the electrode is proportional to the energy of the electrons available from it and is amenable
to control by an electrical circuit called a potentiostat. At negative potentials, the potentiostat places an
excess negative charge on the electrode, which raises the energy of the available electrons and makes the
electrode a strong reductant. At positive potentials, there is an excess positive charge; hence electrons
are stabilized on the electrode and it acts as a strong oxidant. All intermediate degrees of oxidizing and
reducing power are available within the practical extremes of potential set by oxidation and reduction of
the solvent system or the electrode itself. In general, there is a working range of 1-6 volts in a given
medium.
Experimentally, it is convenient only to describe the energy of available electrons, or the Fermi level, in
a relative sense. That is, one compares their energy on the electrode of interest (the working electrode)
against their energy on a reference electrode, which is a chemical system of constant composition, so
that it provides a stable, reproducible, electrically meaningful reference. The difference in electron
energies between the two electrodes is just the voltage difference between them. That voltage is
measured and controlled by the potentiostat. The most widely used reference electrode is the saturated
calomel electrode (SCE),

Hg/Hg2Cl2/KCl (aqueous, sat'd)

so one usually sees potentials quoted as V vs. SCE. In these experiments, you will use a silver/silver
chloride reference electrode,

Ag/AgCl/KCl (aqueous, sat'd)

Since its potential is -0.045 V vs. SCE, the potential scales based on these two electrodes are offset from
each other by 45 mV. In other words, a working electrode at +0.500 V vs. SCE is at +0.545 V vs.
Ag/AgCl; and an electrode at -1.00 V vs. SCE is also at -0.955 V vs. Ag/AgCl.
If the electrode is tuned over a wide potential range, one can expect it to do oxidations in the more
positive regions, perhaps no electrochemistry at all in an intermediate zone, and reductions at more
negative potentials. If the electrode oxidizes a compound, such as ferrocene,

FeII(Cp)2 FeIII(Cp)2+ + e- (on the electrode)

A11
electrons are taken from the species in solution and are deposited on the electrode. This charge removal
must be compensated by a reduction at a second electrode elsewhere in the system. That electrode is
called a counter electrode. Its function usually is only to preserve electroneutrality; the reactions
happening there are not of interest in most cases. The overall effect of doing desired electrochemistry at
the working electrode is to cause electron flow across its interface with the solution, then to pass the
charge through an external circuit to the counter electrode, where it crosses again into the solution via an
electrode reaction opposite to that at the working electrode. Ions move in solution to maintain local
electroneutrality in that phase. Figure 1 shows a block diagram of an electrochemical cell. Figure 2
shows all of these processes for a system in which ferrocene is oxidized at the working electrode to
ferricenium. Figure 3 shows a typical electrochemical cell used in cyclic voltammetry.

i i

reference working
COUNTER electrode electrode
REFERENCE
POTENTIOSTAT
E WORKING

i i

Figure 1

teflon cap
- +
-
- e
e
auxiliary electrode

Ox - FeCp 2
counter electrode working
+ electrode
Red FeCp 2+

stir bar
ion movements

Figure 2 Figure 3

The standard reduction potential (E0) for ferrocenium/ferrocene in a particular solvent is a measure of
the energy required for the electrochemical reaction. It is a thermodynamic quantity and is related to the
Gibbs free energy change (G) by the following equation where n is the number of electrons transferred
and F is the Faraday, a constant.
G = -nFE0

It is useful to think of the standard potential as the boundary between two zones of stability. At more
positive values, only the oxidized form is stable at the electrode surface, but at potentials more negative
that E0, only the reduced form is stable. The transition region through E0 is a few kT wide (perhaps 100

A12
mV at room temperature; kT=25.6 meV at 298 K). These ideas are embodied in Figure 4, which uses
E0 for the couple DPA/DPA- as an example.

Figure 4.

The flow of current in the external circuit is easily measured and describes the electrochemical process.
Its magnitude is directly proportional to the rate of reaction at the working electrode; thus is can reflect
the kinetics of steps in the electrode process, including the rate constants for transfer of electrons to and
from the electrode, for adsorption or desorption of species at the interface, or for reactions in solution
that comprise parts of the overall electrode reaction. Very often it also reflects the rate at which the
electroactive species is brought to the electrode by mass transfer. Many analytical applications stress
conditions in which the current is controlled only by mass transfer. In most modern diagnostic methods
the solution is not stirred, and mass transfer is limited to diffusion, which can be described very well
from a theoretical standpoint. If high rates of conversion are desired, stirring may be employed.
Oxidations imply that electrons flow from the solution into the electrode, whereas reductions require a
flow of electrons from the electrode to a solution species at the electrode surface. We will regard
oxidation currents (anodic currents) as negative and reduction (cathodic) currents as positive. This
convention is arbitrary, but is widely used in the literature.

Since current flow is generally required, the solution must be ionically conducting. It always has a
supporting electrolyte, whose purpose is to improve conductivity and perhaps to control pH or act as a
ligand. The solvent must be sufficiently polar that the electrolyte dissociates appreciably. Typical
solvents are water, methanol, ethanol, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, and
methylene chloride. In this experiment, you will use methylene chloride with tetra-n-butylammonium

A13
hexafluorophosphate (TBAH) as supporting electrolyte. The working range is about +1.8 V to -1.7 V
vs. SCE. You will use a small platinum disk as a working electrode in unstirred solutions. This
arrangement assures that you will have mass transfer only by diffusion along the single axis normal to
the surface, as required for application of the theory that you will employ. The counter electrode is
small Pt helix. Working and counter electrodes are also frequently made from gold, graphite, glassy
carbon and mercury.

There is a strictly functional relationship between current and potential. One cannot control both.
Setting the potential defines the current and vice versa. The potentiostat operates as shown in Figure 2.
It senses the voltage difference between the working and counter electrodes and forces current as
required through the working and counter electrodes, so as to maintain the sensed voltage difference at
the programmed value.

Cyclic Voltammetry
If one scans the potential of the working electrode over a range of potentials one can expect to see a
current response reflecting the various oxidation and reduction processes that are possible within that
interval. The method is called voltammetry because it involves recording current vs. potential. It is
cyclic because one sweeps the potential at a constant rate from an initial value to some limit, then
reverses direction and scans back to the initial point. A response curve is shown in Figure 5 for a
solution containing 1 mM thiathrene (TH) and 1 mM 2,5-diphenyl-1,3,4-oxadiazole (PPD) in
acetonitrile with 0.1 M TBAP. The scan starts at -1.0 V vs. SCE, proceeds at 100 mV/sec toward
negative potentials. At -2.5 V the scan reverses. At +1.5 V there is a second reversal, and the scan
continues to -1.0 V, where it stops.

A14
 Figure 5. Cyclic voltammogram of thiathrene (TH) and 2,5-diphenyl-1,3,4-oxadiazole (PPD) in acetonitrile.

The response in Figure 5 is interpreted as follows: As the potential moves from -1.0 V to -2.2 V, very
little current flows because nothing in the solution is electroactive in this range. Beyond -2.2 V there is
a cathodic current rise PPD is reduced to PPD., an anion radical. As the scan continues, a peak is
observed at -2.3 V, then the current falls because electrolysis has depleted the region near the electrode
of PPD. Thus the rate of its diffusion to the electrode slows down, and the current reflects the
corresponding decreased rate of reduction. Reversal of the scan at -2.5 V causes the potential to move
positively again, and one soon reaches the threshold where the electrode first became capable of
reducing PPD to the anion radical. At still more positive values, the PPD. that was just generated is
reoxidized by the electrode, so an anodic peak develops. The anodic current eventually decays to zero
(i.e., as the scan continues from -2.2 V toward positive potentials) because all of the PPD. in the
diffusion layer near the electrode is collected back again by diffusion. The average of the cathodic and
anodic peak potentials Epc and Epa is very close to the standard potential E0 for the PPD/PPD. couple.

As the scan in Figure 5 continues between -1.8 V and 1.0 V vs. SCE, there is again a region of
electroinactivity, but at +1.1 V an anodic current rises as TH is oxidized to TH., its cation radical. A
peak again appears as the diffusion layer is depleted of TH, and reversal of the scan produces a cathodic
peak as TH. is recollected from the diffusion layer and reduced. When the scan returns to the starting
potential of -1.0 V, the region near the electrode has been restored essentially to its initial condition.

One of the most useful features of cyclic voltammetry is its ability to generate a potentially reactive
species and then to examine it immediately by reversal. The responses in Figure 5-5 are for two

A15
systems, TH and PPD, that produce completely stable ion radicals. One can tell that by examining the
ratio of reverse (r) and forward (f) peak currents. For example, for the PPD/PPD. peaks, ipc is the
forward peak current, and ipa is the reverse one. For a stable product ipr/ipf = 1. Note from Figure 5-5
how the reverse peak current is measured. If PPD. were not completely stable, but decayed to an
electroinactive product, then the anodic peak would be smaller because less PPD. would have survived
in the diffusion layer until reoxidation could take place. If none survived because the following
reactions was very fast, then there would be no current peak on reversal and ipa/ipc=0. Even so, at a
faster scan rate, one might still be able to catch a glimpse of the PPD. in the form of a measurable ipa.
At a very fast scan rate, one might even be able to see PPD. essentially as a stable species with ipa/ipc =
1, because one would then generate and reoxidize the species before it had a chance to decay at all.
Scan rate is the important time-related variable in cyclic voltammetry. It can extend form ~10 mV/sec
to 2000 V/sec with fast potentiostatic and recording apparatus, but with x-y recorders, the fastest scan is
about 1 V/sec.

A16
 Appendix III--Multiplets in NMR Spectroscopy

This appendix will introduce the theory behind multiplet splitting patterns. We will attempt to
explain the distribution and intensities of the peaks of the quintet observed in acetone-d6 due to
some residual impurity of acetone-d5 (CD3C(O)CD2H) that occurs at ca. 1.3 ppm in its 1H NMR
spectrum.

Initially we have to introduce some rules. The nuclear spin quantum number, I, may have
integral or half integral values (0, 1/2, 1, 3/2, ...) and is a characteristic value for a given nucleus.
The magnetic quantum number, m, for a given nucleus can have values I, I-1, I-2, ..., -I (or a total
of 2I + 1 values). A typical example is 1H which has a value of I = 1/2. In this case m can take
the values 1/2, -1/2. Another example is D (or 2H) which has I = 1. In this case m can take the
values 1, 0, -1.

The 'n + 1 rule' taught in many courses to explain multiplicity (or splitting patterns of peaks) is a
simplified version of the more general formula 2nI + 1. The number of lines observed for
coupling to n equivalent nuclei of spin I is 2nI + 1. These lines will be equally spaced by a
distance J (in Hertz) that is a characteristic value for the nuclei involved. For example, the
proton spectrum of a molecule containing a 10BH unit (eg. 10BH4-) ,where the proton is coupled
to one (n = 1) nucleus with I = 3, would exhibit a splitting pattern of 7 lines (2nI + 1 = 2(1)(3) +
1 = 7) each separated by a distance of J(10B1H) Hz (the nuclei involved in the splitting are put in
parenthesis).

The intensities of the peaks can be explained with a probability argument. Suppose we have a
proton coupled to two equivalent protons (I = 1/2). We expect 2nI + 1 = 3 lines (a triplet) spaced
J(1H1H) Hertz apart. The values that m can take on for an I = 1/2 nucleus are 1/2 and -1/2.
Now, we have to consider that both the nuclei can be simultaneously 1/2 and 1/2; or they can be
different 1/2 and -1/2 and similarly -1/2 and 1/2. If we add the values of m for each set of possi-
bilities we get a value called m. If both are m 1/2, then m = 1. If both are m = -1/2, then m
= -1. If one is m = 1/2 and the other is m = -1/2 or one is m = -1/2 and the other is m = 1/2, then
m = 0. We can construct the following table.

Table A-1
m Possible spin combinations Number of spin combinations
1 (1/2, 1/2) 1
0 (1/2,-1/2), (-1/2,1/2) 2
-1 (-1/2,-1/2) 1

A17
The final column lists the number of possible spin combinations which add up to m. The
greater the number of spin combinations possible that add up to a certain m, the greater the
probability that the nuclei will have that value of m. That is, statistically, in our example we
have a better chance of seeing m = 0 than we do seeing m = 1 or -1. This relates to intensities.
The intensity of a particular peak in a multiplet is directly proportional to the probability of
seeing the corresponding value of m. The proton in our example will thus appear as a 1:2:1
triplet, which corresponds to the number of spin combinations for the two other nuclei when m
= 1, 0, and -1.

Exercise

1. Explain how the 'n + 1 rule' used in 1H NMR spectroscopy is a simplification of the more
general 2nI + 1 rule.
2. Calculate the expected number of lines, and the intensities of those lines, for a multiplet
due to the coupling of a proton to two equivalent deuterium nuclei (I = 1). Compare the
experimental results (the provided spectrum) with the theoretically predicted results.
Note: construct a table like Table A-1.

A18