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CHEM311-232 - Chapter 35-Part1

The document discusses different topics in physical chemistry including quantum mechanics, spectroscopy, statistical mechanics, transport phenomena, chemical kinetics, thermodynamics and reaction rates. It describes methods for determining the order of reactions and integrating rate laws to evaluate reaction kinetics numerically. Various physical methods for experimentally measuring chemical reaction rates are also outlined.

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20 views22 pages

CHEM311-232 - Chapter 35-Part1

The document discusses different topics in physical chemistry including quantum mechanics, spectroscopy, statistical mechanics, transport phenomena, chemical kinetics, thermodynamics and reaction rates. It describes methods for determining the order of reactions and integrating rate laws to evaluate reaction kinetics numerically. Various physical methods for experimentally measuring chemical reaction rates are also outlined.

Uploaded by

bsbak631
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© © All Rights Reserved
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Textbook: Physical Chemistry, 3rd Edition, Thomas Engel and Philip Reid,

Part I:
Quantum Mechanics
Spectroscopy, &
Part II:
Statistical Mechanics &
Transport Phenomena
Part III:
Chemical Kinetics
• FIRST MAJOR
• SECOND MAJOR
• FINAL EXAM
• CLASS WORK
•
•
•
•

•
•
•
•
•
•
•
 Thermodynamics described the
reaction is spontaneous by
involving Gibbs or Helmholtz
energy
 Chemical kinetics monitored
rate of reaction, which can
provide an insight into the In this reaction, kinetic is the
reaction mechanism process to find rate of changes of
either A or B concentration by time
 The time evaluation of the reactants and products
is quantified by differentiating both sides of this
equation that give rate of reaction definition
For example:
The rate expression should be …..
Note:
-ve sign is given to rate based on
reactants to make rate of +ve all time
•

Extensive properties, depend on the amount of matter.


Intensive properties, do not depend on the amount of matter.

Solution:
for ideal gases, P = nRT/V, where n/V = [i] = P/RT
Thus the rate should be given by
R = -1/ni . d[i]/dt
= -1/nCH3CHO . d[CH3CHO]/dt
= -1/RT . dPCH3CHO/dt
•

•
 For the reaction
4 NO2(g) + O2(g)  2 N2O4(g)
 The experimentally determined rate is

 Thus the reaction is 2nd order with respect to NO2 and 1st order with
respect to O2 , thus the reaction is 3rd order.
 Since the rate is always has unit of conc./time, it is possible to use
the relation of rate law and order to identify the unit of the rate
constant that gives
 Rate Law order Unit of k
R=k zero order M.s-1
R = k [A] 1st order s-1
R = k [A]2 2nd order M-1.s-1
R = k [A][B] 2nd order M-1.s-1
 35.3.1 Measuring Reaction Rate
 For a general reaction
 The rate equation is

 Thus the rate is the tangent for the


concentration curve at a specific time as
shown in the given plot …….
For example, at t = 0, k = 40 1/s and [A] = 1M, the Rt=0 = 40 M/s
while at t = 30, k = 40 1/s and [A] = 0.3M, the Rt=30 = 12 M/s
it is clear that the rate of reaction varied with time, where it is decreased with time.
 Therefore “initial rate” is used to compare different reactions
 Initial rate is the rate of reaction before the reaction concentration has undergo any
change from its initial value
 With a known k, [A]0, and the order of the reaction one can determine the rate of
reaction at any time.
 35.3.1 Determining Reaction Order
 For the reaction
 The general rate equation is
an equation with several unknowns
 To solve for the unknowns “a and b” one of the following two
strategy can be adopted:
 Strategy I: Isolation Method
In this method all reactant except one should be in excess,
e.g., if [A] = 1.0 M and [B] = 0.01M, by the end of reaction 0.99 M of A is
remaining, thus [A] can be assumed constant to make the rate equation

Thus the rate only depends on [B]-variation, using a plot the order of [B]
can be obtained using numerical methods ….
Same process can be applied for A by using B in excess, and so on
 35.3.1 Determining Reaction Order
 For the reaction
 The general rate equation is
an equation with several unknowns
 To solve for the unknowns “a and b” one of the following two
strategy can be adopted:
 Strategy II: Initial Rate Method
In this method all initial reactant
concentration except one kept constant
and by using initial rate of two sets order
of the variable reactant can be identified,
Example 35.2
Using the following data set, determine the [A] [B] Initial Rate
orders of A and B and the rate constant of the
reaction 2.3 x 10-4 3.1 x 10-5 5.25 x 10-4
4.6 x 10-4 6.2 x 10-5 4.20 x 10-3
9.2 x 10-4 6.2 x 10-5 1.68 x 10-2
Solution: a = 2, b = 1, and k = 3.16 x 108 M-1s-1
The question now: How can we determine the rate of chemical reaction
experimentally? (Could be via Chemical or Physical Method)
Via Chemical Method:
 This method can be used for long timescale “slow” reaction, i.e., in
hours, days or years.
In this method, the reaction should be terminated or stop after starting at
different time intervals by
- Rapid cooling (called questioning technique)
- Adding another chemicals that react fast will all species except one
Then analysis is performed to identify the remaining amount of reactants
Via Physical Method:
 In this method is used for “fast” reactions in milli-, micro-, nano-sec.
Most of the modern kinetic methods are involved such as:
- Spectroscopy,
- Optical properties, ..
The advantages; no other chemicals used, fast reactions could be monitored
For example, the thermal decomposition of:
PCl5 (g)  PCl3 (g) + Cl2 (g)
produced two gaseous molecules from one, which
means the measure of pressure of reaction in a
pressure container with a fixed volume should provide
direct information about reaction kinetics, where [A] ~
P at constant T,
at ……. t = 0, Pi = P0
at ……. t = t, Pt = (P0-Px)+2Px = P0+Px
and, Px = Pt – P0

Other physical methods, such as the “Stopped-Flow Techniques” which


can be used for fast timescale within 10-3 s reaction.
In this process, the reaction is monitored at the mixing chamber once it
starts via a spectroscopy such as Visible spectroscopic method as seen
in the above Figure
35.5 Integration Rate law Expressions
 Many reactions cannot be studied by the initial rate methods
because the instability of reactants or the timescale, therefore a
numerical method could be used to evaluate the kinetics of them.
 Integrated rate law is used to prove the order numerically and
then predict the reaction rate constant, e.g.,
35.5.1 First Order Reactions:
35.5 Integration Rate law Expressions
 Where the relation between the product
concentration and the initial concentrations
can be summarized as ………………
 The linear form of the 1st order reaction is

Where the slope is -k and the intercept ln [A]0


35.5.2 Half-life and 1st order
 “Half-Life” is the time required for the
reactant concentration to decrease to “1/2”
of its initial value to give
35.5 Integration Rate law Expressions
Example 35.3
The half-life of a 1st order decomposition reaction is 2.05 x 104 s, how
long will it take for the reactant to decay to 60% of its initial value?
Answer:
k =(ln2/t1/2) = 3.38 x 10-5 s-1
when [A] = 0.6[A]0, ln([A]/[A]0) = -3.38 x 10-5 t, t = 1.51 x 104 s
Example 35.4
14C is a radioactive nucleus with a half-life of 5760 years, which has
15.3 decay per min for a dead material. This decay can be used to
determine how old is it. For a piece of fossilized wood that has 2.4 14C
decay event per min, the age of this fossilized wood could be
k =(ln2/t1/2) = 3.81 x 10-12 s-1 and
[14C]/[14C]0 = 2.4 /15.3 = 0.157, then
ln (0.157) = - 3.81 x 10-12 s-1 t, t = 4.86 x 1011 s
35.5 Integration Rate law Expressions
35.5.3 Second Order Reactions (Type I):
Two cases are considered for this type of reactions as follows:
 Type I: Bimolecular or two uni-molecular of identical initial
concentration [A]=[B], then

35.5.4 “Half-Life” and reactant of type I……………


35.5 Integration Rate law Expressions
35.5.5 Second Order Reactions:
Type II: two uni-molecular of different initial concentration [A]≠[B], then

Note: t1/2 concept is not applied to Type II, unless reactants are mixed in
stoichiometric proportion (1:1), then it become type I
THQ-Q5A
Q01

Q02

Q03
Q04

Q05

Due Date
28/04/2024
12:00 am

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