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Kinetics Outline

Kinetics Outline

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in timechangeBoionconcentratin thechange Brespect towithrate Average
=
sM023.0s0s20 M0.000.46MRateAvg
==
Chapter 14. Chemical Kinetics
Common Student Misconceptions
It is possible for mathematics to get in the way of some students’ understanding of the chemistry of this chapter.Students often assume that reaction orders may be determined from stoichiometric coefficients.Students often confuse intermediates and transition states.Students often confuse adsorption and absorption.
Lecture Outline
14.1 Factors that Affect Reaction Rates
Chemical kinetics
is the study of how fast chemical reactions occur.There are several important factors which affect rates of reactions:physical state of the reactants,concentration of the reactants,temperature of the reaction, andpresence or absence of a catalyst.The goal is to understand chemical reactions at the molecular level.
14.2 Reaction Rates
The speed of a reaction is defined as the change that occurs per unit time.It is often determined by measuring the change in concentration of a reactant or product withtime.The speed of the chemical reaction is its
reaction rate
.For a reaction A
BHere the change in the concentration of B is defined as:
(concentration of B) = (concentration of B at final time)
(concentration of B at initial time)Illustrate this with an example:Suppose A reacts to form B. Let us begin with 1.00
A.At
= 0 (time zero) there is 1.00
A and no B present.At
= 20 sec, there is 0.54
A and 0.46
B.At
= 40 sec, there is 0.30
A and 0.70
B.We can use this information to find the average rate with respect to B:For the reaction A
B there are two ways of measuring rate:
min002 )s0atBof (Conc)20atBo(ConcB)(Conc RateAvg
====
 s s
 
[ ] [ ] [ ] [ ]
 Dc Bb Aa
====
1111 Rate
Chapter 14
the rate of appearance of product B (i.e., change in moles of B per unit time) as in the precedingexample, andthe rate of disappearance of reactant A (i.e., the change in moles of A per unit time).Note the negative sign! This reminds us that rate is being expressed in terms of thed
isappearance
of a reactant.A plot of number of moles versus time shows that as the reactants (A) disappear, the products (B)appear.
Change of Rate with Time
In most chemical reactions we will determine the reaction rate by monitoring a change inconcentration (of a reactant or product).The most useful unit to use for rate is molarity.Since volume is constant, molarity and moles are directly proportional.Consider the following reaction:C
4
H
9
Cl(
aq
) + H
2
O(
)
C
4
H
9
OH(
aq
) + HCl(
aq
)We can calculate the average rate in terms of the disappearance of C
4
H
9
Cl.The units for average rate are mol/L
s or 
M/s
.The average rate decreases with time.We can plot [C
4
H
9
Cl] versus time.The rate at any instant in time is called the
instantaneous rate.
It is the slope of the straight line tangent to the curve at that instant.Instantaneous rate is different from average rate.It is the rate at that particular instant in time.For our discussion we will call the "instantaneous rate" the rate, unless otherwiseindicated.
Reaction Rates and Stoichiometry
For the reaction:C
4
H
9
Cl(
aq
) + H
2
O(
)
C
4
H
9
OH(
aq
) + HCl(
aq
)The rate of appearance of C
4
H
9
OH must equal the rate of disappearance of C
4
H
9
Cl.What if the stoichiometric relationships are not one-to-one? For the reaction:2HI(
 g 
)
 
H
2
(
 g 
) + I
2
(
 g 
)The rate may be expressed as:We can generalize this equation a bit.For the reaction:
aA + bB
cC + dD
The rate may be expressed as:
177
 A
=
][RateAverage
[ ] [ ]
==
OHHCClHC Rate
9494
[ ] [ ] [ ]
===
22
IHHI21Rate
 
Chemical Kinetics
14.3Concentrationand Rate
In general, rates:increase when reactant concentration is increased.decrease as the concentration of reactants is reduced.We often examine the effect of concentration on reaction rate by measuring the way in which reactionrate at the beginning of a reaction depends on starting conditions.Consider the reaction: NH
4+
(
aq
) + NO
2 – 
(
aq
)
N
2
(
 g 
) + 2H
2
O(
)We measure initial reaction rates.The initial rate is the instantaneous rate at time
= 0.We find this at various initial concentrations of each reactant.As [NH
4+
] doubles with [NO
2 – 
] constant the rate doubles.We conclude that the rate is proportional to [NH
4+
].As [NO
2 – 
] doubles with [NH
4+
] constant the rate doubles.We conclude that the rate is proportional to [NO
2 – 
].
The overall concentration dependence of reaction rate is given in a
rate law
or rate expression.For our example, the rate law is:Rate =
[NH
4+
][ NO
2 – 
]The proportionality constant
is called the
rate constant
.Once we have determined the rate law and the rate constant, we can use them to calculate initialreaction rates under anyetof initial concentrations.
Exponents in the Rate Law
For a general reaction with rate law:Rate =
[reactant 1]
m
[reactant 2]
n
The exponents
m
and
n
are called
reaction orders
.The
overall reaction order
is the sum of the reaction orders.The overall order of reaction is
m + n +
For the reaction: NH
4+
(
aq
) + NO
2 – 
(
aq
)
N
2
(
 g 
) + 2H
2
O(
)The reaction is said to be first order in [NH
4+
], first order in [NO
2 – 
], and second order overall.Note that reaction orders must be determined experimentally.They do not necessarily correspond to the stoichiometric coefficients in the balanced chemicalequation!We commonly encounter reaction orders of 0, 1 or 2.Even fractional or negative values are possible.
Units of Rate Constants
Units of the rate constant depend on the overall reaction order.For example, for a reaction that is second order overall:Units of rate are:Thus the units of the rate constant are:
178
( )( )
2
ionconcentratoUnitsconstantrateoUnitsrateoUnits
=
1122
ion)concentrato(Units rate)o(UnitsconstantrateoUnits
===
s s

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