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Reaction Rates
Section 14.1
– milk spoiling
Concentration
– iron rusting
Temperature
• What controls the rate? Presence of a
Catalyst
Physical State
2
Basic Concepts
Section 14.2
3
Expression of Rate
Section 14.2
Rate = Δ[CH3OH]
Δt Brackets represent
the concentration in
Molarity;
Δ indicates change
1
4
Reaction Rates
Section 14.2
Rate = Δ[CH3OH]
Δt
The negative sign indicates a
rate of disappearance.
5
Relationships Between Rates
Section 14.2
− − + +
negative negative positive positive
6
Example
Section 14.2
Time, min
Ti i [H+],
] M
0.0 1.85
79.0 1.67
158.0 1.52
316.0 1.30
632.0 1.00
2
7
Rate Comparisons
Section 14.2
• Average rate
• Instantaneous rate
8
Average Rate
Section 14.2
2.00
This line intersects the
1.75 curve at two points.
The slope gives the
[H + ] (M )
1 50
1.50
average rate over an
1.25 interval of time.
Δy
1.00
Δx
0.75 Δy
m=
Δx
0 100 200 300 400 500 600 700
Time (min)
9
Instantaneous Rate
Section 14.2
1 50
1.50
[H + ] (M
3
10
Example Question
Section 14.2
PROCESS:
- Draw a tangent line to the curve at each point.
- Select two points on the tangent line and determine
their (x,y) coordinates.
- Calculate the slope of the line.
11
Solution
Section 14.2
2.00
1.75
[H + ] (M )
1 50
1.50
1.25
1.00
0.75
0 100 200 300 400 500 600 700
Time (min)
12
Stoichiometry and Rates
Section 14.2
4
13
Stoichiometry and Rates
Section 14.2
14
Stoichiometric Relationships
Section 14.2
aA + bB → cC + dD
15
Example
Section 14.2
Δ[H2] 3 Δ[NH3]
=
Δt 2 Δt
5
16
Example
Section 14.2
17
Solution
Section 14.2
1 Δ[N2O5] Δ[O2]
• For O2, =
2 Δt Δt
18
Concentration and Rates
Section 14.3
6
19
Rate Laws
Section 14.3
Rate = k[reactants]
20
Rate Laws
Section 14.3
21
Example
Section 14.3
7
22
Example Data
Section 14.3
Δ[S2O82-]
Exp [S2O82-] [I−]
Δt
1 0 038
0.038 0 060
0.060 1 4 x 10-55
1.4
23
Example Questions
Section 14.3
24
Example
Section 14.3
8
25
Example Questions
Section 14.3
QUESTIONS:
26
First Order Reactions
Section 14.4
A → products
Rate = k[A]
y = mx + b
27
Example
Section 14.4
9
28
Graph 1
Section 14.4
600
500
NC), mmHg
400
The graph of pressure
Pressure (CH3N
100
0
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, sec
29
Graph 2
Section 14.4
6.50
6.00
ln (P ressu re (C H 3 N C ))
5.50
slope = -k
5.00
4.50
4.00
3.50 intercept = ln[A]0
3.00
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, sec
30
Example
Section 14.4
PROCESS:
- To determine the rate constant, must calculate the
slope
- To determine the half-life for the reaction, need
more background information
10
31
Graph 2
Section 14.4
6.50
6.00
ln (P ressu re (C H 3 N C ))
5.50
5.00 ((0,6.22)
, )
4.50
4.00
3.50
3.00
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, sec
(15,000, 3.11)
32
Half-life
Section 14.4
If t1/2 = 12 seconds….
t=0 t = 12 t = 24 t = 36 t = 48 t = 60
33
Derivation
Section 14.4
ln [[A]]t = - kt + ln [[A]]0
½ [A]0
ln = - kt½
[A]0
11
34
Derivation Continued
Section 14.4
½ [A]0
ln = - kt½
[A]0
1
- ln = kt½ The half-life for a
2
first-order reaction
is NOT dependent
0.693 = kt½
on concentration.
t½ = 0.693
k
35
Solution to Example
Section 14.4
t½ = 0.693
k
36
Example Problem
Section 14.4
12
37
Second Order Reactions
Section 14.4
A → products
Rate = k[A]2
1 1
= ktt +
[A]t [A]0
1
Plot on the y-axis and time on the x-axis
[A]t
38
Graphical Analysis
Section 14.4
39
Nuclear Chemistry
Section 21.1
13
40
Complete Atomic Symbols
Section 2.3
mass number
X
atomic number
5 protons
For example,
11
5 B 5 electrons
41
Isotopes
Section 2.3
1 2 3
1H 1H 1H
42
Definitions
Section 21.1
• Nuclide
– A nucleus with a specified number of
protons and neutrons
• Radionuclides
– Nuclei that are radioactive
• Radioisotopes
– Atoms containing radionuclides
14
43
Types of Radioactive Decay
Section 21.1
44
Radioactive Decay
Section 21.1
Radioactive decay –
238 234
92U → 90Th + 24He
NOTE:
238 = 234 + 4 92 = 90 + 2
45
Example
Section 21.1
235
92U + 01n → 160
62
Sm + 72
30
Zn + ___ 01n
239
94Pu + 01n → 144
58
Ce + _____ + 2 01n
15
46
Example Calculation
Section 14.4
47
Reaction Mechanisms
Section 14.6
48
Example
Section 14.6
Rate = k[NO2]2
Proposed Mechanism:
NO2(g) + NO2(g) → NO3(g) + NO(g)
NO3(g) + CO(g) → NO2(g) + CO2(g)
16
49
Molecularity
Section 14.6
50
Intermediates
Section 14.6
NO2(g) 2( ) → NO3(g)
2( ) + NO2(g) 3( ) + NO(g)
( )
NO3(g) + CO(g) → NO2(g) + CO2(g)
51
Reaction Mechanisms
Section 14.6
17
52
First Criteria
Section 14.6
53
Second Criteria
Section 14.6
54
Collision Model
Section 14.5
18
55
Energetics of a Reaction
Section 14.5
56
The Arrhenius Equation
Section 14.5
Ea
• An increase in
RT the Ea results in
k = Ae
a decrease in k
A = frequency factor • An increase in T
results in an
increase in k
-Ea 1
ln k = + ln(A)
R T
linear equation with a slope of –Ea/R
and a y-intercept of ln(A)
57
Catalysis
Section 14.7
• A catalyst is a substance
that speeds up a reaction
without begin consumed
itself.
• Lowers the activation
energy of the reaction by
providing an alternative
pathway.
• Does not affect the ΔH.
• Can be a homogeneous
catalyst or a heterogeneous
catalyst.
19
58
Catalysis Example
Section 14.7
59
E-Instruction Question
60
E-Instruction Question
A 0.35
B 7.0 x 10-3
C 3.5 x 10-3
D 1.8 x 10-3
E 3.5 x 10-5
20
61
E-Instruction Question
N2 + 3 H2 → 2 NH3
A the same
B two times
C half
D three times
62
E-Instruction Question
63
E-Instruction Question
21
64
E-Instruction Question
A a curve.
B a straight line with a negative slope.
C a straight line with a positive slope.
65
E-Instruction Question
A 6.25
B 12.5
C 25
D 50
66
E-Instruction Question
Cl + O3 → ClO + O2
O + ClO → Cl + O2
A ClO
B Cl
C O3
22