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Chemical Kinetics CH 290
Chemical Kinetics CH 290
6/2/2008
15/07/23 09:48
CH 344: CHEMICAL KINETICS AND
ELECTROCHEMISTRY (2 units)
Dr. E.B. Mubofu and G. Kinunda
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ASSESSMENT MODE:
1. Set of questions to be distributed for the tutorials
2. There will be 2 tests, each carry 20 Marks
3. Final examination: 60 Marks
Section A: 30 Marks
Section B: 30 Marks, 3 Questions answer 2
References:
1. P.W. Atkins Physical chemistry (5th, 6th or 7th
ed.)
2. G.M. Barrow Physical chemistry 3rd ed. 1973 or
later ed.
3. B. G. Segal Chemistry experiment and theory, 1985
4. Any advanced physical chemistry book
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Collision Theory
6/2/2008
15/07/23 09:48
• The pharmacokinetics of artensunate is that
following oral administtration …….. reaches Cmax
within 45 to 90 minutes. The product is ………
effective against malaria by the same mechanism
of action.
15/07/23 09:48
•You may recall that thermodynamics can predict whether
or not a reaction will proceed but cannot tell us how fast
or slow will the reaction occur! NOW
• Chemical kinetics deals with the understanding of
the factors that affect the rate of a chemical
reaction and elucidates information about the
mechanism of the reaction
• (A reaction mechanism is a series of steps that defines the order
in which bonds are broken and new ones are formed, until the
final product is obtained)
• chemical reaction kinetics is concerned with the
rates at which chemical reactions occur
• NB: Generally, a rate is a change in some quantity wrt time
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What factors affect the rate of a chemical reaction?
• Nature of reactants: Each reaction proceeds at its own rate.
Changing the nature of reactants will, in general, change the
rate of the reaction
• The concentration of reactants: For a chemical reaction to
occur, the reactants must come close together and collide.
Because collisions are more frequent when concentrations
increase, then the reaction rates increase as the concentration
of the reactants increase
• The temperature: In general, increasing the temperature
increases the rate of the reaction. The rate of most reactions
increases by a factor of 2 or 3 for a 10oC rise in temperature!
• The nature of the solvent:Although not all reactions occur in
solution, but for those carried in solution, changing the solvent
will generally change the rate of the reaction
• The presence of the catalyst
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Molecular reaction dynamics
• Why do reactions occur?
• How?! i.e pathways and rate/speed
• This is the heart and the cornerstone of chemistry
(why?) because here we examine the details of
what happens to molecules at the climax of
reactions and hence we can establish mechanisms
of reactions
• The simplest quantitative account of reaction rates at
microscopic level is in terms of collision theory which
can be used only for discussion of reactions between
simple species in the gaseous phase
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Collision Theory of bimolecular gas reaction
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Collision Theory
• In other words, collision theory maintains that the
rate constant for a reaction is the product of three
factors.
1. Z, the collision frequency
2. f, the fraction of collisions with sufficient energy to
react
3. p, the fraction of collisions with the proper
orientation to react
4. Mathematically,
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Collision frequency
or
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This implies that the higher the temperature, the higher the root mean square
speed of the molecules, and at a given temperature heavy molecules travel
more slowly than light molecules
c T/M
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A collision will only be successful
only if the kinetic energy exceeds a
minimum energy value, a of
the
reaction THUS
The rate constant should also be
proportional to a Boltzmann factor
Ea
anticipate that
-Ea/RT
k2 (T/M)e
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Moreover, not every collision will
lead to reaction even if the energy
requirement is satisfied, because the
reactants may need to collide in a
certain orientation. The steric
requirement suggests that another
factor, p, should be introduced, and
-Ea/RT
thus k2 p(T/M)e
Indeed this is what is predicted by the collision theory!
It reflects that for a successful reaction/effective
collision:-
k2 encounter rate x minimum energy x steric requirement
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Collision Theory-Collision energy
• That is, f, the fraction of molecules with
sufficient threshold energy turns out to be very
temperature dependent.
• This is the primary factor relating temperature increases to
observed rate increases.
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Collision Theory and reaction rates
• The reaction rate dependence on the
fraction of collisions with the proper
orientation, p, is independent of
temperature changes
• So, with changes in temperature, Z and p
remain fairly constant.
• We can thus use that fact to derive a
mathematical relationship between the rate
constant, k, and the absolute
temperature.
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The Arrhenius Equation
• If we were to combine the relatively
constant terms, Z and p, into one constant,
and call it A. We obtain the Arrhenius
equation:
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The Arrhenius Equation
• It is useful to recast the Arrhenius equation
in logarithmic form.
y = b +mx
• A plot of ln k versus (1/T) should yield a straight line with a slope
of (-Ea/R) and an intercept of ln A.
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The Arrhenius Equation
• A more useful form of the equation emerges
if we look at two points on the line this
equation describes that is, (k1, (1/T1)) and
(k2, (1/T2)).
• With this form of the equation, given the activation
energy and the rate constant k1 at a given
temperature T1, we can find the rate constant k2
at any other temperature, T2.
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Now, let us compare k2 = NAp(T/M)e-Ea/RT with
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Note: The above equation has the Arrhenius form
k2 =Ae-Ea/RT AND
• We therefore identify the activation energy with the
minimum kinetic energy along the line of approach that is
needed for a reaction and
• That the pre-exponential factor A is a measure of the rate of
collisions occurring in gas
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Collision rates in gases-The collision frequency z
NOTE: = Collision cross-section =d2 (Fig
below), and d = 1/2(dA + dB)
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END
END
END
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CH344
13/2/2008
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A Simple approach to calculate the collision frequency Z of the
molecules we consider the following hypothetical ‘collision tube’
Fig. 1
A: Freeze the positions of all molecules except one
B: Note what happen when the mobile molecule travels through the gas with
a mean speed C for a time t
C: Upon travelling, the molecule sweeps out a ‘collision tube’ of cross-
sectional area = d2 and length Ct and thus volume = Ct
miss
hit
d >d
<d hit
Fig 1
<d
hit >d <d
Collision cross-section
15/07/23 09:48 miss
•The number of stationary molecules with centres
inside the collision tube is given by the volume of the
tube times the number density (N = NA[A] ) and is
NCrelt = NA[A] Crelt
The collision frequency (the number of collisions per unit time) is
therefore NA[A] Crel where [A] = the molar concentration of
molecule A, NA = the Avogadros constant and Crel = is the relative
mean speed of the molecules
For collision between different types of molecule, the
mean relative speed is
Crel = (8kT/μ)1/2 where μ = reduced mass = mAmB/mA + mB
Thus the collision frequency is
ZAB= (8kT/μ)1/2 NA2[A][B] and for similar molecules
the collision frequency is ZAA= (8kT/μ)1/2 NA2[A]2
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The energy requirement
• According to collision theory, the rate of change in [A]
molecules results from the collision density and the
probability that a collision occurs with sufficient energy
d A
dt = -{ 0 rel f()d}NA[A][B]
k2 = NA 0 rel f()d
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• Assuming that the reactive collision cross-section is zero
below a, then we see that the variation of reactive cross-
section () with energy is expressed by
a
= ( 1 - )
• THUS k2 = NACrele-Ea/RT
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The steric requirement: Consider the Arrhenius
parameters in the table below
2NOCl
→ 2NO + 2Cl 9.4 X109 5.9 X 1010 102.0 0.16
→
2ClO
Cl 2 + O2 6.3 X 107 2.5 X 1010 0.0 2.5 X 10-3
H2 + C2H4→
C 2H 6 1.24 X 106 7.4 X 1011 180.0 1.7 X 10-6
K + Br2→
KBr + Br 1.0 X 1012 2.1 X 1011 0.0 4.8
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The Arrhenius parameters data in the table above
show that :
• There is a fair agreement between theory and
experiment
• There are discrepancies
• There are some cases where there are several orders
of magnitude smaller than experimental
• It therefore shows that the collision energy is not the only
criterion for reaction and that some other feature such as
the relative orientation of the colliding species is important
• NB: Larger than theory implies the reaction occurs more
quickly than the particles collide
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•The disagreement between theory and experiment
is accommodated by introducing a steric factor, p,
and expressing the reactive cross-section, σ*
A
as a multiple of the cross-section, σ* = pσ = σ A
exp
Theory
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SCT : a summary.
• The major problem with SCT is that the threshold
energy a is very difficult to evaluate from first
principles.
• The predictions of the collision theory can be critically
evaluated by comparing the experimental pre-
exponential factor with that computed using SCT.
• We define the steric factor P as the ratio between
the experimental and calculated A factors.
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• We can incorporate P into the SCT expression for the
rate constant.
• For many gas phase reactions P is considerably less
than unity.
• Typically SCT will predict that Acalc will be in
the region 1010-1011 L mol-1s-1 regardless of
the chemical nature of the reactants and products.
• What has gone wrong? The SCT assumption of hard
sphere collision neglects the important fact that
molecules possess an internal structure.
• We need a better theory that takes molecular
structure into account. The activated complex theory
does just that .
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Transition state theory (TST) = Activated complex
theory (ACT) = Absolute rate theory
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END
END
END
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CH344
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RECAP: SCT HAS WEAKENESSES!
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RECALL:
An activated complex forms between reactants as they
collide and begin to assume the nuclear and electronic
characteristic of products
We know that the change in potential energy associated
with formation of the activated complex accounts for the
activation energy of the reaction
ACT considers a more detailed calculation of rate
constants using the concept of statistical thermodynamics
END
END
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CH344
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Thermodynamic aspects of TST
The concept of an equilibrium between reactants and the
activated complex enables us to treat activation processes in
terms of thermodynamic functions
If we accept K in the Eyring equation as an equilibrium
constant, then we can express it in terms of a Gibbs energy of
activation, G through the definition
G RTInK or G RTInK p
Where
G = G (activated complex) - G (reactants)
o o
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G
Thus K= Kp e= RT
and therefore from Eyring equation
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HOW?
Now from the formal definition of activation energy,
E a RT 2 In k , then gives E H 2 RT for reactions in gases
T a
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So substituting H in the rate equation we get
kT RT 2 S R Ea RT
k2 ee e
h p
in gases
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Furthermore, H U pV where for reactions occurring
kT RT S R H RT kT RT S R U RT
k2
e e
e e
h p h p
and in gas phase
kT RT S R H RT kT RT S R n U RT
k2
e e
e e e
h p h p
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When compared with the empirical Arrhenius equation
Ea
k 2 Ae RT
, we then see that in gases, the frequency factor
kT RT 2 S R
e e
A= h p for gases
While for reactions in solution
kT RT S
ee R
A= h p
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If reactants are only atoms or simple molecules, then
there is a relatively small amount of rearrangement of
energy among the various degrees of freedom in the
activated complex
Consequently, S will be either a small positive or
S
negative number, so that e R and thus steric factor p is
close to unity. This implies that the reaction will proceed
much faster than predicted by the collision theory
END
END
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CH344
27/2/2008
15/07/23 09:48
• The pharmacokinetics of artensunate is that
following oral administtration …….. reaches Cmax
within 45 to 90 minutes. The product is ………
effective against malaria by the same mechanism
of action.
15/07/23 09:48
•You may recall that thermodynamics can predict whether
or not a reaction will proceed but cannot tell us how fast
or slow will the reaction occur! NOW
• Chemical kinetics deals with the understanding of
the factors that affect the rate of a chemical
reaction and elucidates information about the
mechanism of the reaction
• (A reaction mechanism is a series of steps that defines the order
in which bonds are broken and new ones are formed, until the
final product is obtained)
• chemical reaction kinetics is concerned with the
rates at which chemical reactions occur
• NB: Generally, a rate is a change in some quantity wrt time
15/07/23 09:48
What factors affect the rate of a chemical reaction?
• Nature of reactants: Each reaction proceeds at its own rate.
Changing the nature of reactants will, in general, change the
rate of the reaction
• The concentration of reactants: For a chemical reaction to
occur, the reactants must come close together and collide.
Because collisions are more frequent when concentrations
increase, then the reaction rates increase as the concentration
of the reactants increase
• The temperature: In general, increasing the temperature
increases the rate of the reaction. The rate of most reactions
increases by a factor of 2 or 3 for a 10oC rise in temperature!
• The nature of the solvent:Although not all reactions occur in
solution, but for those carried in solution, changing the solvent
will generally change the rate of the reaction
• The presence of the catalyst
15/07/23 09:48
•Reactions we would like to speed up.
–Drug delivery
–Paint drying
–Destruction of air pollutants in auto exhaust
–Most industrial chemical processes
–Breakdown of synthetic plastics in land fill sites
etc.
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To get the picture of rate in chemical kinetics let us
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More elaboration on definition of rate
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Rate law
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General rate expression: rate = = k[A]m[B]n….
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•For homogeneous gas-phase reactions, it is often more
convenient to express the rate law in terms of partial pressures,
which are related to molar concentrations by
Pj = RT[A] thus, = f(PA, PB …)
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– Predict the rate of reaction from the composition of the
mixture
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Units of rates and rate constant
• The units of the rate of any reaction are
moles per liter per unit time, which may be
mol.L-1s-1.
• The units the rate constant, k, however,
depend on the order of the reaction
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END
END
END
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CH344
7/3/2006
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Determination of reaction order
• Before anything can be said about the mechanism of a reaction, the first task is
to determine the order of the reaction. This can be achieved by several methods
such as isolation, differential, half-life, integrated and relaxation methods.
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Differential method (suggested by van’t Hoff in 1884!)
• Since rate = = k[A]n, then by taking logarithms of
both sides, we obtain
• log = nlog[A] + logk
– Then by measuring at different concentration of A, we
can obtain the value of n from a plot of log versus log[A]
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log[A]
Integration method
NOTE: Zeromethod
Integration order isreactions are
an obvious relatively
procedure rare , you
whereby among the best
measure the
studied reactions are those that occur on metal surfaces
concentration of the reactant(s) at various time intervals of a reaction and
15/07/23 09:48
Plots for a zero order reaction
concentration of A Time
The expression [A] = [A]oe-kt shows that in a first-order reaction, the reactant
concentration decreases exponentially with time with a rate determined by k
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•Plots for first order reaction
k Slope = -k
In[A]/[A]o
Rate
concentration of A Time
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• The first expression shows
that a plot of 1/[A] vs t should
give a straight line with slope
=k
• The last expression lets us
predict the concentration of
A at any time after the start
of the reaction. It also shows
that the conc. of A
approaches zero more
slowly than in a first -order
reaction with the same initial
15/07/23 09:48 rate
d A
= -k[A][B]
dt
Note: The above rate law cannot be intergrated until we know how the concentration of B
is related to that of A.
Now consider the reaction A + B P where P denotes product and [A]o and [B]o are
initial concentrations for A and B respectively.
From the stoichiometry of the reaction, it follows that when the conc. of A has fallen to
[A]o –X, the conc. of B will also have fallen to [B] o –X because for each A that
disappears entails the same disappearance of one B. It follows that
d A d A dx
= -k([A]o –x )([B]o- x) but because = - , the rate law becomes
dt dt dt
dx
= k([A]o –x )([B]o- x)
dt
dx
Thus = kdt
([ A]o x)([ B]o x)
15/07/23 09:48
with the initial condition that x = 0 when t = 0 and so the integration of the rate law by
partial fractions gives In
[ B]
[ B]
o
= ([B]o – [A]o)kt
[ A]
[ A]o
Half Lives
The half life of a substance (reaction) is the time taken for
the concentration of the reactant to fall to half its initial
concentration
• This simple method is done by determining the dependence
of the half-life of a reaction on the initial concentration,
using the half life equation(s) from integrated rate laws.
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Half Lives
0.693
k
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Unlike in the first order, the half-life of a substance in a
second-order reaction varies with the initial concentration
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Relaxation methods
• The term relaxation denotes the return of a system to equilibrium
• relaxation = return of a system to equilibrium
• Relaxation methods are used to measure rate constants.
• Apply a sudden perturbation to the equilibrium, e.g., a
temperature jump or a pressure jump, and monitor the relaxation
• Let us consider the response of a reaction rates to a sudden
change in temperature
• Recall that the equilibrium composition of a reaction depends on
the temperature (provided rH is nonzero), thus a shift in
temperature acts as a pertubation on the system [normally done
by LASER or microwave discharges)
15/07/23 09:48
When a sudden temperature increase is applied to
a simple A B equilibrium that is first-order in
each direction it can be shown that the
composition relaxes exponentially to the new
equilibrium composition:
• The exponential relation is
given by
t
x = xo e
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END
END
END
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CH344
13/3/2006
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Reactions approaching equilibrium/Opposing reactions
• The rate laws we have considered so far disregard the
possibility that the reverse reaction is important , and none of
the laws describes the overall rate when the reaction is close
to equilibrium
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NB: This equation is very important in chemistry
because it relates the thermodynamic quantity, the
equilibrium constant, K, and the quantities relating to
rates i.e If one of the rate constants can be measured,
then the other may be obtained if the equilibrium
constant is known.
For a more general reaction, the overall equilibrium constants for all the intermediate
stages of the reaction mechanism is
k1 k 2
K = x x ……
k 1 k 2
Where the ks are the rate constants for the individual steps and the k - are for the
respective reverse steps
15/07/23 09:48
•The discussion of the relationship between reaction rates and
equilibria has its roots in a principle of great importance in
chemical kinetics and is called the principle of microscopic
reversibility!
• The principle states that at equilibrium the rates of the
forward and reverse process are equal for every elementary
reaction occurring
• This means that the process A B is exactly balanced by B A so
that the equilibrium cannot be maintained by a cyclic process, with the
reaction being A B and A C A on the opposite direction
• The usefulness of this principle in chemical kinetics is that it tells us that
the reaction pathway for the reverse of the reaction is opposite of the
pathway for the forward reaction!
• What does it mean when related to TST?
This means that the transition states (i.e the complex between the reactants
and products along the reaction pathway) for the forward and reverse reactions
are identical.
15/07/23 09:48
Consecutive elementary reactions
Some reactions proceed through a formation of an
intermediate (I) (i.e species that occur in the reaction
mechanism but do not appear in the overall reaction
as in the consecutive unimolecular reactions
b a
b a
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If the three concentrations are plotted against time we
get the following figure
• We see that:
– Reactant A decays by
an ordinary first-order
– intermediates rises to a
maximum at tmax and
then falls to zero
– The concentration of
the product P rises from
zero and reaches [A]o
[p] = {1 + k e k kk e }[A]o
kb t k at
a b
b a
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•Generally, the rate determining step is the slowest step in a
mechanism and controls the overall rate of the reaction.
• NOTE: The rate determining step is not just the slowest step:
it must be slow and crucial gateway for the formation of
products! If a faster reaction can also lead to products, then the
slowest step is irrelevant because the slow reaction can then be
side-stepped (see Fig below)
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The rate determining step (RDS)
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•The rate law for a reaction with a rate determining step can
often be written down almost by inspection.
• For instance, if the first step in the reaction mechanism is rate
determining step, then the rate of the overall reaction is equal
to the rate of the first step because all subsequent steps are
so fast that once the first intermediate is formed it results
immediately in the formation of products (Fig below).
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Pre-equilibrium
• We have dealt with a mechanism of a simple consecutive
reaction. NOW
• What happens if the intermediate reaches an equilibrium with
the reactants say A and B?:
ka kb
A+B I P
k'a
• This reaction involves pre-equilibrium, in which an
intermediate is in equilibrium with the reactants
NOTE: A pre-equilibrium arises when the rates of
formation of the intermediate and its decay back into
reactants are much faster than its rate of formation of
products, thus, the condition is possible when k' a >> kb
but not when kb >> k'a
• Because we assume A, B and I are in equilibrium, then
15/07/23 09:48 K = [I]/[A][B], K = ka/k'a
•The rate of formation of product P may therefore be
written d[P]/dt = kb[I], But [I] = K[A][B]
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END
END
END
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CH344
14/3/2006
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The steady-state approximation
• You may have noticed a considerable
increase in mathematical complexity as
soon as the mechanism has more than a
couple of steps
• One approach to solving these complex
reactions is to integrate the rate laws
numerically and an alternative approach is
to make an approximation!
• This approximation is termed steady-
state approximation and it assumes
that, after an initial induction period,
an interval during which the
concentrations of intermediates, I,
rise from zero, and during the major
part of the reaction, the rates of
change of concentrations of all
reaction intermediates are negligibly
small i.e d [ I ] 0
dt
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For instance, we can apply the approximation to the
consecutive first-order mechanism.
RECALL THAT
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Homework: Use the steady-state approximation to devise the rate law
for the decomposition of N2O5,
N2O5 (g) 4NO2 (g) + O2 (g)
on the basis of the following mechanism.
ka
N2O5 NO2 + NO3
k'a
kb NO2 + O2 +NO
NO2 + NO3
kc
NO + N2O5 NO2 + NO2 + NO2
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•Catalytic reactions consist of a reaction cycle formed by a
series of elementary reaction steps for example DA reaction
R
N
O
+
N
O
2
4a R = H
4b R = NO2
4c R = OCH3 R
5a R = H
5b R = NO2
5c R = OCH3
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Mechanism of Lewis acid catalysed DA in water
N
O
Cu
2+ O2N
N
NO2
O
2+ O2N
Cu N
O
N
O Cu
2+
NO2
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Rates of catalysed reactions and groups of catalysts:
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END
END
END
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CH344
20/3/2006
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Enzyme kinetics
• One of the most fascinating studies in chemical kinetics is the
investigation of enzyme catalysis
• An enzyme-catalysed reaction is usually characterised by a very
large increase in the rate (on the order of 106 to 1012) and high
specificity
• Specificity means that the enzyme molecule is capable of
selectively catalysing certain reactants, the substrate, while
discriminating against
• An enzyme usually contains one or more ACTIVE SITE(S)
where reactions with substrate take place
• An active site may contain only a few amino acid residue,
residue the
rest of the protein molecule is however required to maintain the
3-D integrity of the network
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In enzymology, we mostly study the basic mathematical
aS
o b S
where a and b are constants
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• The initial rate of product formation o is given by
o =
• Michaelis and Menten assumed that k-1 >> k2 so that the first
step (i.e the formation ES complex) can be treated as a rapid
equilibrium process AND therefore the dissociation constant
is given by k
K s 1
E S E o ES S
k1 ES ES
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Solving for [ES], we obtain
[ ES ]
E o S
K s S
d[ P] k 2 E o S aS
we get o compare with
dt K s S b S
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END
END
END
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CH344
21/3/2006
15/07/23 09:48
If you postulate a short time after the enzyme and the substrate are mixed,
the concentration of the enzyme-substrate will reach a constant value can
you apply SSA? Yes you can! (Briggs and Halden did that in 1925)
d ES
k1 E S k 1 ES k 2 [ ES ]
dt
0 k1 E S k 1 ES k 2 [ ES ]
but E E o [ES ]
0 k1 E o ES S k 1 ES k 2 ES
k1 E o [ ES ]S k 1 k 2 ES
k1 E o S k1[ ES ]S k 1 k 2 ES
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15/07/23 09:48
k 2 E o S k 2 E o S
If we compare S K with K S we see that both equations have
M s
k k 1 1
In this treatment we also define the maximum rate max exactly the same as before such
max S
that max = k 2 E o and hence the above equation can also be written as o
S K M
In principle, this shows that both max and K M can be
determined from a plot of o versus [S] (see Fig.below)
max
KM
15/07/23 09:48
[ S]
• In practice, it is not very useful determining the max since it is
difficult to determine the asymptotic value at a very high
max
substrate concentrations
• A more satisfactory approach is by employing the
Lineweaver-Burk approach where you take a double
max S
reciprocal of equation o S K
M
1 KM 1
o max S max
where
1 1
Versus gives a straight line
o S
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From the plot, K M and max can be obtained from the
slope and intercepts of the straight line.
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What is the significance of max , k 2 and K M ??
The maximum velocity max represents the maximum rate
attainable, that is, it is the rate when the total enzyme concentration
is present as the enzyme-substrate complex!
Enzyme inhibition
15/07/23 09:48
• Enzyme catalysed reactions are prone to inhibition by
molecules that interfere with the formation of the product
Inhibitors are compounds(negative catalysts) that decrease the rate of an enzyme-
catalysed reaction
• Actually, many drugs for the treatment of diseases are
designed to function by inhibiting enzymes!
NOTE: This is one of the strategy towards developing a
drug to treat AIDS. In this case, it involves a steady
administration of a specially designed protease
inhibitor I.e the drug inhibits an enzyme that is key to
the formation of protein envelope surrounding the
genetic material of the human immunodeficiency virus
(HIV). Without a properly formed envelope, HIV can not
replicate in the host organism.
15/07/23 09:48
Enzyme inhibition
There are two types of enzyme inhibitions: Reversible and irreversible
Enzyme Inhibition
Reversible Irreversible
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Competitive Inhibition
• In this case the substrate S and the inhibitor I compete
for the same active site. The reactions are:
E+ S ES P+ E
E+ I EI
1 K I 1 1 1 1
M 1 Thus a straight line is obtained by plotting against at constant I
o max K 1 S max o S
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END
END
END
15/07/23 09:48
CH344
27/3/2006
15/07/23 09:48
Competitive Inhibition
• In this case the substrate S and the inhibitor I compete
for the same active site. The reactions are:
E + S E S P + E
E + I E I
1 K I 1 1 1 1
M 1 Thus a straight line is obtained by plotting against at constant I
o max K 1 S max o S
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15/07/23 09:48
max
S ( o ) inhibition
Dividing equation o max
S K M by K I
1 M 1
we
S K1
o K M I
1
get o inhibition = S K I K M K I
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Noncompetitive Inhibition
E+S ES P+E
E+I EI
ES + I ESI
o I
o inhibition =1+ KI
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UNCOMPETITIVE NHIBITION
An uncompetitive inhibitor does not bind to the enzyme; instead ,
it binds reversibly to the enzyme-substrate complex to yield an
inactive ESI complex. The reactions are:
E+S ES P+E
ES + I ESI
The ESI does not form a product. Again, since I does not interfere
with the formation of ES, uncompetitive inhibition cannot be
reversed by increasing the substrate concentration. The initial rate is
given by
Vmax S ES I
o where KI
KM S 1 I ESI
KI
15/07/23 09:48
The Lineweaver-Burk equation is given by
1 KM 1
1
1
I
o = Vmax S Vmax KI
1 1
A straight line is obtained by plotting o versus S at constant I
S 1
KM 1
1
1
I
Dividing o max
S K M by o Vmax S Vmax KI
we get
o K M S 1 I
KI
o inhibition =
S K M
If conditions are such that [S] >> KM , then the equation becomes
o K M S 1 I I
KI
o inhibition = =1+
S KI
15/07/23 09:48
15/07/23 09:48
The catalytic efficiency of Enzymes
k cat
• The catalytic efficiency, , of an enzyme is the ratio of K M
Now recall that KM
k 1 k 2 and max = k2[E]o
k1
Thus k cat Vmax
X
k1
k1 k 2
KM = = E o k 1 k 2 k 1 k 2
The higher the value of , the more efficient is the enzyme (catalyst).
NOTE: Because k1 is the rate constant for the formation of a complex
from two species that are diffusing freely in solution, the maximum
efficiency is related to the maximum rate of diffusion of E and S in
solution. This happens when k2 >> k-1!
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15/07/23 09:48
END
END
END
15/07/23 09:48
15/07/23 09:48
15/07/23 09:48
Conductance and Conductivity
• The nature of molecular motion in solution can be obtained
by studying the motion of ions in solution (electrolytes).
An electrolyte is an ionic conductor i.e solution, a liquid or a
solid.
Electrolytes dissociate in aqueous solution and the ions
formed act, to a large extent, as free, independent entities (Cf
kinetic-molecular theory of ideal gases)
The ions experience van der Waals forces, interactions of the
ions between themselves and interaction of ions with the
solvent
•By studying the transport of charge through electrolyte
solutions, it is possible to get a picture of how the events occur
and the results can be extrapolated to uncharged (neutral)
species
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The study of this motion of ions is done by measuring the electrical
resistance R, of the solution.
1
The inverse of this resistance, R is the conductance, G, of the
1
solution (units mho or SI unit siemens, S) i.e
1 G
R
Conductance is proportional to the cross-sectional area and is
inversely proportional to length
A A
That is G
l and therefore G
l where conductivi ty
l
Or
A
G Cell constant x G
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The conductivity of the solution depends on the number of ions
present in the solution and we normally introduce the molar
conductivity, m , which is defined as
m where c = the molar concentration of the added electrolyte
c
The concentration dependence of molar conductivities show that
there are two classes of electrolytes i.e Strong and weak
electrolytes
The characteristics of a strong electrolyte is that its molar
conductivity depends only slightly on the molar concentration
(generally decreases slightly as the concentration is increased)
The characteristic of weak electrolyte on the other hand is that its
molar conductivity is normal at concentrations close to zero, but
falls sharply to low values as the concentration increases (Fig
overleaf)
NOTE: The classification is solvent dependent (a solute could be a
weak electrolyte in one solvent but strong in another)
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15/07/23 09:48
STRONG ELECTROLYTES:
Strong electrolytes are substances that are virtually fully ionized in
solution, and include ionic solids and strong acids.
Due to this complete ionization, the concentration of ions in
solution is proportional to the concentration of strong electrolyte
added
At low concentration the molar conductivities m of strong
electrolytes vary linearly with the square root of the concentration:
m om c This variation is called Kohlrausch′s law.
The constant om is the limiting molar conductivity, the molar
conductivity in the limit of zero concentration (when the ions
are effectively infinitely far apart and do not interact with one
another).
The constant is found to depend more on the stoichiometry
of the electrolyte than on its specific identity
15/07/23 09:48
Kohlrausch
′s also showed that om can be expressed as the sum of
contributions from its individual ions
Let us denote the limiting molar conductivity of cations by
and that of anions by then Kohlrausch law of
independent migration of ions states that
om where
and are the numbers of cations and anions per formula unit of
electrolyte (e.g 1 for HCl or NaCl where 1, 2 for
MgCl2)
WEAK ELECTROLYTES
Weak electrolytes are not fully ionized in solution.
The marked concentration dependence of their molar conductivities
arises from the displacement of the equilibrium towards products at
low molar concentrations.
HA (aq) + H2O (l) H3O+(aq) + A (aq)
15/07/23 09:48
a H O a A
Ka 3
a HA
The conductivity depends on the number of ions in solution, and
therefore on the degree of ionization, , of the electrolyte; and
for weak acids, we talk of the degree of deprotonation.
For the acid HA at a molar concentration c, at equilibrium
[H3O+] = c, [A-] = c, [HA] = (1- )c
Ignoring activity coefficients, the acidity constant Ka, is
approximately
2c
Ka
1 from which it follows that
1
K 4c 2
a 1 1
2c K a
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The acid is fully protonated at infinite dilution, and its molar
conductivity is then om . Because only a fraction is actually
present as ions in the actual solution, the measured molar
o
conductivity m m with given above.
15/07/23 09:48
1
This shows that a plot of m against c m , then the intercept at c = 0
1
will be om as shown in the figure below.
1 1 mc
o
m m K a om 2
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END
END
END
15/07/23 09:48
15/07/23 09:48
THE MOBILITIES OF IONS
Why ions move at different speed? Why they have different molar
conductivities and why the molar conductivities of strong
electrolytes decrease with the square root of the molar concentration?
We shall see these when we study the drift speed, the ion mobility
and the transport numbers!
The drift speed:
When the potential difference between two electrodes a distance
l apart is ∆, the ions in the solution between them experience a
uniform electric field of magnitude E where
l
In this field, an ion charge ze experiences a force of magnitude
ze
F zeE
l
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NOW: A cation responds to application of the field by accelerating
to the negative electrode and the anion responds by accelerating to
the positive electrode
However, as the ion moves through the solvent, it experiences a
frictional retarding force, Ffric, proportional to its speed.
Assume Stokes formula for a sphere of radius a and speed s
applies at microscopic scale, then we can write this retarding
force as
Ffric = fs, where f = 6a and s = speed
The two forces act in opposite directions, and the ions quickly
reach a terminal speed, the drift speed when the accelerating
force is balanced by the viscous drag.
zeE
s
The net force is zero when f
It follows that the drift speed of an ion is proportional to the
strength of the applied field. We write s uE
15/07/23 09:48 where u is called the mobility of the ion
Recall that
zeE zeE
s ............................1
f 6a
s uE........................2
Comparing equation 1 and 2 we get
ze ze
Mobility, u
f 6a
Ionic mobilities in water at 298 K, u/(10 -8 m2 s-1V-1)
H+ 36.23
+
Na 5.19
+
K 7.62
Zn2+ 5.47
-
OH 20.64
-
Cl 7.91
Br- 8.09
SO2-4 8.29
15/07/23 09:48
After this bond cleavage has taken place, and the released
molecule has rotated through a few degrees (a process that takes
about 1 ps), there is a rapid adjustment of bond lengths and
angles in the remaining cluster, to form an H5O2+ cation of
structureH2O· · ·H+ · · ·OH2 (Fig. b).
03/04/2006 5:27
15/07/23 09:48
Shortly after this reorganization has occurred, a new H 9O4+
cluster forms as other molecules rotate into a position where they
can become members of a secondary hydration sphere, but now
the positive charge is located one molecule to the right of its
initial location (Fig. c).
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15/07/23 09:48
Transport numbers/Transference
t o o
m
o o
For each type of ion t m
15/07/23 09:48
Conductivities and ion-ion interactions
15/07/23 09:48
Ionic atmosphere causes (1) relaxation effect (2) Electrophoretic
effect
To accommodate the effect of motion, the picture of an ionic
atmosphere looks as a spherical haze of charge
The ionic atmosphere based on Debye-Huckel theory in that there is
a tendency for anions to be found around cations and of cations to be
found around anions (cicled to emphasize). Note: The ions are in
ceaseless motion, and the figure represents a snapshot of their
motion.
15/07/23 09:48
Now because the ions forming the atmosphere do not
adjust to the moving ion immediately, the atmosphere is
incompletely formed in front of the moving ion and
incompletely decayed behind the ion(Fig)
15/07/23 09:48
The overall effect is the displacement of the centre of charge of
the atmosphere a short distance behind the moving ion
Because the two charges are opposite, the result is a retardation of
the moving ion and this reduction of the ions is what we call the
relaxation effect
Another effect on the ionic atmosphere in the motion of ions is
that because moving ions experience a viscous drag; the drag is
enhanced because the ionic atmosphere moves in the opposite
direction to the central ion
The enhanced viscous drag is called the electrophoretic effect
and reduces the mobility of the ions, and hence also reduces their
conductivities AND
It can therefore be shown that the decrease in molar conductivity
due to these two effects is proportional to the square root of
concentration!!
15/07/23 09:48
A quantitative formulation is rather complex. Debye-Huckel-
Onsgager theory attempts to obtain the quantitative
expression.
The theory leads to a Kohlrausch-like expression in which
= A + B om
with
1
1 3
2
z eF 2
2 2 qz F 2 2
A B
3 RT 24RT RT
where = electric permittivity of the solvent
q = 0.586 for 1,1-electrolyte
NOTE: The slopes of the conductivity curves are predicted to depend
on the charge type of the electrolyte, in accord with Kohlausch law,
and comparisons between theory and experiment agree quite good at
very low concentration (0.001 M) depending on the charge type (Fig)
15/07/23 09:48
04/04/2004 20:47
15/07/23 09:48
Ionic atmosphere causes (1) relaxation effect (2) Electrophoretic
effect
To accommodate the effect of motion, the picture of an ionic
atmosphere looks as a spherical haze of charge
15/07/23 09:48
Many macromolecules, such as DNA, are charged and move
in response to an electric field . This motion is called
electrophoresis. Electrophoretic mobility is a result of a
constant drift speed, s, reached by an ion when the driving
force zeE (where, as usual, ze is the net charge and E is the
field strength) is matched by the frictional force fs.
zeE zeE
s
f 6 a
Therefore, the mobility of a macromolecule in an electric
field depends on its net charge, size (and hence molar
mass), and shape. The latter two factors are implied by the
dependence of s on f. in the above equation.
15/07/23 09:48
Electrophoresis is a very valuable tool in the separation of
biopolymers from complex mixtures, such as those resulting
from fractionation of biological cells. We shall consider three
techniques commonly used: viz gel elctrophoresis, capillary
electrophoresis and isoelectric focusing. They differ in the
manner in which the drift speeds of biomolecules are
controlled in order to achieve separation of a mixture into its
components.
Gel Electrophoresis
In gel electrophoresis, migration takes place through a gel slab. A
common gel material for the study of proteins is cross-linked
polyacrylamide. In most cases, the goal of the experiment is to
separate a sample according to the molar masses of its
components. However, the drift speed formula, states that the
shape and charge will also determine the drift speed. For example,
proteins with the same size but different net charge travel along the
slab at
15/07/23 different speeds.
09:48
One way to avoid this problem and to effect a separation by
molar mass is to denature the proteins in a controlled way.
Sodium dodecyl sulphate is an anionic detergent that is very
useful in this respect: it denatures proteins, whatever their
initial shape, into rods by forming a complex with them.
Isoelectric Focusing
Naturally occurring macromolecules acquire a charge when
dispersed in water. An important feature of proteins and other
biopolymers is that their overall charge depends on the pH of
the medium.
15/07/23 09:48
For instance, in acidic environments protons attach to basic
groups and the net charge is positive; in basic media the net
charge is negative as a result of proton loss. At the isoelectric
point, the pH is such that there is no net charge on the
biopolymer. Consequently, the drift speed of a biopolymer
depends on the pH of the medium, with s = 0 at the
isoelectric point.
Isoelectric focusing is an electrophoresis method that
exploits the change of drift speed with pH. Consider a
mixture of distinct proteins dispersed in a medium with a pH
gradient along the direction of an applied electric field. Each
protein in the mixture will stop moving at a position in the
gradient where the pH is equal to the isoelctric point. In this
manner, the protein mixture can be separated into its
components.
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END
END
END
15/07/23 09:48
15/07/23 09:48
RECAP
You may recall from chemical equilibrium topic that the
equilibrium expression is not strictly constant if concentrations are
used as the measure of ‘active masses’ of the reacting species.
Strong electrolytes though completely dissociate into ions in the
solid state, do not behave as though the ions are independent
particles in aqueous solutions.
As you may remember, the physical properties of salt solutions,
such as conductivity and freezing point, suggest that the ions may
be ‘clustered’ together, with positive ions having more negative
than positive ions in their immediate neighbourhood, and negative
ions in turn having an excess of positive ions around them (IONIC
ATMOSPHERE).
This time-averaged, spherical haze around the central ion, in which
counter ions outnumber ions of the same charge as the central ion, has a
net charge equal in magnitude but opposite in sign to that on the cenral
ion, and
15/07/23 09:48is called its ionic atmosphere
Ion activities:
Under such conditions, the effectiveness of ions in
determining the rate of chemical reactions, and also in
altering physical properties of the solvent, is less than it
would be were each ion capable of acting independently.
Only in very dilute solutions are ions sufficiently free of the
influence of neighboring ions to act as independent
particles.
In order to obtain agreement between experimental and
theoretical equilibrium, the chemist multiplies actual
concentrations (e.g. molalities, molarities) by certain
numbers, called activity coefficients , to obtain effective
concentrations, called activities a.
The activity of a species A is defined as follows: a = [A].
From this definition, it can be seen that the more ideally a
solution behaves, the closer the activity coefficient to unity.
Indeed,
15/07/23 09:48 at infinite dilution,
=1 and a = [A].
Alternatively,
The activity a is a kind of ‘effective’ mole fraction of the
b
solution and is related to the molality, b by a b where
activity coefficient, , depends on the composition,
molality, and temperature of the solution.
As the solution approaches ideality (in that it obeys Henry’s
law) at low molalities, the activity coefficient tends towards
1.
b
1 and a as b 0
b
There is an enormous amount of experimental evidence to
indicate that electrostatic between ions and between ions and
solvent molecules can cause large differences between activity
and concentration. Such interactions are general, not just
between ions undergoing chemical reaction.
15/07/23 09:48
For example, many compounds show increased solubility in the
presence of electrolytes containing no ions which react chemically
with ions of the precipitate! The solubility product constant, Ksp, of
BaSO4, for instance, increases from 1.0 x 10-10 in water to 2.9 x 10-
10
in 0.010 M aqueous KNO3 at 298 K. Clustering of NO-3 ions
about Ba2+ and of K+ ions about SO 2-4 tends to shield Ba2+ and SO
2-
4 ions from each other and to hamper their effectiveness in forming
BaSO4
15/07/23 09:48
Note: The geometric mean of activity coefficient of monovalent
1
2
solution is
Generally, for a salt with ions like Mn+ Xm-, the geometric mean
activity is
1/ n m
n m
15/07/23 09:48
The Debye-Huckel Limiting law
The long range and strength of the Coulombic interaction
between ions means that it is likely to be primarily responsible for
the departure from ideality in ionic solution and to dominate all
other contributions to nonideality
This possible domination is the basis of the Debye-Hckel theory
of ionic solutions (Peter Debye and Erich Hückel 1923)
A qualitative account of the theory is given
Oppositely charged ions attract one another. As a result, anions
are likely to be found near cations in solution, and vice versa
NB: Overall, the solution is electrically neutral, but near any
given ion there is an axcess of counter ions i.e Averaged over
time, counter ions are more likely to be found near any given ion
15/07/23 09:48
END
END
END
15/07/23 09:48
15/07/23 09:48
The Debye-Huckel Limiting law
The long range and strength of the Coulombic interaction
between ions means that it is likely to be primarily responsible for
the departure from ideality in ionic solution and to dominate all
other contributions to nonideality
This possible domination is the basis of the Debye-Hückel theory
of ionic solutions (Peter Debye and Erich Hückel 1923)
A qualitative account of the theory is given
Oppositely charged ions attract one another. As a result, anions
are likely to be found near cations in solution, and vice versa
NB: Overall, the solution is electrically neutral, but near any
given ion there is an axcess of counter ions i.e Averaged over
time, counter ions are more likely to be found near any given ion
15/07/23 09:48
The Debye-Huckel Limiting law
DH theory is a quantitative theory of electrolyte solution which
is based on a rather simple model and allows us to calculate the
quantity of activity coefficient from the basic properties of
the solution.
The mathematical details of DH’s treatment are too difficult
to present here rather a simple underlying assumptions will
be presented.
Debye and Huckel began by assuming the following:
1. Electrolytes are completely dissociated into ions in
solution
2. The solutions are dilute, that is, the concentration is
0.01 m or lower
3. On the average each ion is surrounded by ions of
opposite charge , forming the ionic atmosphere
15/07/23 09:48
The Debye-Huckel Limiting law
Working from these assumptions, Debye and Huckel calculated the
average electric potential at each ion caused by the presence of other
ions in the ionic atmosphere.
The Gibbs free energy of the ions was then related to the
activity coefficient of the individual ion.
15/07/23 09:48
The Debye-Huckel Limiting law
Since most studies are carried out in water at 298 K (we have
= 78.54 and T = 298 K) and the above equation
becomes.simplified as written below:
The model leads to the result that at very low concentrations the
activity coefficient can be calculated from the Debye-Hückel
limiting law
1
log 0.509 z z AI 2
15/07/23 09:48
It is important to realise that the sum extends over all the ions
present in the solution! For instance, a solution consisting two
types of ion of molalities b and b
1
I
2
b z 2 b z 2 / b
Note: The ionic strength emphasizes the charges of the ions because
the charge numbers occur as their squares!
15/07/23 09:48
APPLICATION OF DH THEORY
The DH limiting law can be applied to study the solubility of
proteins. How soluble the protein is in the aqueous solution
depends on the temperature, pH, dielectric constant, ionic
strength, and other characteristics of the medium.
We shall only be concerned with the influence of ionic strength.
Suppose we want to investigate the effect of ionic strength on the
solubility of AgCl. The dissolution process is
AgCl(s) Ag+ (aq) + Cl (aq)
o
The thermodynamic solubility product for the process,
K sp is
o
K a Ag aCl -
sp
o
15/07/23 09:48 K bAg Ag bCl - Cl
sp
Because, activity, a = molality x activity coefficient!
o
But K Ag Cl K sp
sp
S
Hence log S o 0.509 z z I
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The solubility of solute may increase or decrease with the
increase of ionic strength.
15/07/23 09:48
Extended Debye-Huckle limiting law
The simple DH equation, or limiting law, has been found to
give useful results only in dilute solutions. As the ionic
strength increases, mean activity coefficients calculated from
the equation are significantly smaller than the experimental
value.
For example, the calculated value for the mean activity
coefficient in 0.10 M HCl is 0.69, whereas the experimental
value is 0.8!
Debye and Huckel later extended their theoretical treatment,
assuming that ions are not point charges, but have significant
size, and that they are present in solutions of greater ionic
strength than originally assumed. They derived the so called
extended Debye-Huckel equation,
15/07/23 09:48
0.512Z A Z B I
log
1 B I
where is the diameter of the ion in angstrom (1 Å= 10 -10 m), and B
a term which depends on the absolute temperature and the dielectric
constant of the solvent.
Its value at 298 K using the dielectric constant for pure water is
0.328. The term , sometimes called the ion-size parameter, is
said to correspond to the distance of closest approach of the
cation and anion.
Note: Activity coefficients calculated by the extended DH
equation are in good agreement with experimentally measured
mean values up to ionic strengths of about 0.1. For solution of
higher ionic strength, a number of modifications of the DH
equation have been proposed.
15/07/23 09:48
The energy, and therefore the chemical potential, of any given
central ion is lowered as a result of its electrostatic interaction
with its ionic atmosphere.
This lowering of energy appears as the difference between the
ideal
molar Gibbs energy Gm and the ideal value G m of the solute,
and hence can be identified with RT ln .
NB:The stabilization of ions by their interaction with their ionic
atmospheres is part of the explanation as to why chemists
commonly use dilute solutions, in which the stabilization is less
important, to achieve precipitation of ions from electrolyte
solutions. In other words, as the solution becomes diluted, the
solute becomes increasingly stabilised and the practical
consequence of this is that it is very difficult to remove traces of a
solute from such a solution!
15/07/23 09:48
Example: Q. Calculate the mean activity coefficient , of 5.0
x10-3 molkg-1 KCl(aq) at 298 K.
1
1 b
But I b b / b
=
2 b
Where b is the molality of the solution (note b- = b+ = b) and
therefore we have
1
1
b 2
log 0.509 I 0.509
2
b
1 1
log 0.509 I 0.509 5 x10
2
3 2
= -0.036
log
Hence = 0.92
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END
END
END
15/07/23 09:48
Lecture on 2 May 2006
15/07/23 09:48
Electrochemistry
• Electrochemistry is the science which deals with
the consequences of the transfer of electric charge
from one phase to another.
• Electron transfer occurs at interfaces between a
metallic conductor (an electrode) and an ionic
conductor (an electrolyte).
• •An electrochemical reaction is a heterogeneous
process which involves electron transfer across a
phase boundary or interface.
•Electrochemical reactions are labelled as redox
(Reduction / oxidation) processes.
•Oxidation is the loss of electrons (LEO) and
Reduction is the gain of electrons (GER).
15/07/23 09:48
Why do we study electrochemistry?
•Every battery is an electrochemical cell and indeed the
measure of its voltage is a Gibbs free energy indicator.
•In nerve impulses in biological systems there are
electrochemical potentials
•Concentration gradients across cell and other membranes
cause electrochemical potential differences.
•In manufacturing and chemical etching, electrochemical
reactions abound.
•Photosynthesis, where carbon is fixed in living matter is a basic
electrochemical process
•The transport of oxygen in blood by hemeogloblin and the
change of the oxidation states of iron involves electrochemistry
•Therefore:A basic understanding of the principles behind
electrochemical processes to understand all these processes is
needed.
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Know
The
Differen
ces
Betwe
en
These!
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Basic Concepts
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END
END
END
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Lecture on 8 May 2006
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An overview of electrochemical cells (RECAP):
Electrochemical cells are grouped based on the general
thermodynamic nature of the reaction (i.e expressed as
whether the change in Gibbs energy is -ve or +ve)
A galvanic cell uses a spontaneous reaction inside it (-∆G ) to
generate electrical energy) i.e The reacting system does work
on the surrounding and all batteries are voltaic!
An electrolytic cell on the other hand uses electrical energy to
drive a non-spontaneous reaction (+∆G) i.e The surroundings
do work on the reacting system
It is important to note that all electrochemical cells have
several common features:Have two electrodes (Anode and
Cathode) and the oxidation half-reaction takes place at the
anode and the reduction half-reaction takes place at the
cathode
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Shorthand nomenclature
• Rather than writing out the full chemical
equation, we use a shorthand notation:
Salt bridge
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Cell reaction
2+
Left hand electrode: Zn (aq) + 2e- Zn(s) .....2
Hence the overall cell reaction is the difference i.e eqn 1 - eqn 2 resulting into
2+ 2+
Cu (aq) + Zn(s) Cu(s) + Zn (aq)
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THE CELL POTENTIAL
A cell in which the overall cell reaction has not reached
chemical equilibrium can do electrical work as the reaction
drives electrons through an external circuit
The work that a given transfer of electrons can accomplish
depends on the potential difference between the electrodes
The potential difference is called the cell potential and is
measured in volts, V
When the cell potential (potential difference) is large, a given
number of electrons travelling between the electrodes can do a
large amount of electrical work and vice versa
A cell in which the overall reaction is at equilibrium can do no
work, and the cell potential is zero
The resulting potential difference when the cell (not the cell
reaction) is at equilibrium is what is called the electromotive
force 09:48
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THE CELL POTENTIAL
From thermodynamics, the maximum electrical work that a system
(the cell) can do is given by the value of ∆G, Welec., max = ∆G
(RECALL: The reaction Gibbs energy, ∆rG, is defined as the slope of
the graph of the Gibbs energy plotted against the extent of reaction)
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Nernst equation:
We can extend the relation of the emf to the activities of the
participants in the cell reaction
(Recall: , where Q is the reaction quotient)
NOW
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A concentration cell is a galvanic cell in which the
electrode materials and the solutions in both half-cells are
composed of the same substances; only the
concentrations of the two solutions differ
Consider a concentration cell where the solution M has L
and R molalities
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Because a cell cannot drive a
current through a circuit when the two electrode
compartments are identical! (i.e ∆
rG = 0 ).
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We know that a galvanic cell is a combination of two
electrodes , and each one can be considered as making a
characteristic contribution to the overall cell potential
Because it is impossible to measure the contribution of a single
electrode, we define the potential of one electrode as zero and
then assign values to others on that basis
OR
NOTE
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Applications of Standard Potentials:
Cell emfs are a convenient source of data on the Gibbs
energies, enthalpies and entropies of reactions
NOTE: