Beruflich Dokumente
Kultur Dokumente
13.1
13.2
13.3
13.4
Rates of Chemical
Reactions
Rates of Chemical Reactions
Expressions of Reaction Rates in Terms of
Rates of Changes in Concentrations of
Reactants or Products
Methods of Measuring Reaction Rates
Factors Affecting Reaction Rates
Chemical Kinetics
A study of
(1) reaction rates
(2)
(3)
reaction mechanisms
Explosive reactions
2H2(g) + O2(g) 2H2O(l)
Vigorous reactions
2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
Q.1
+
10
Slow reactions
Fermentation of glucose
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g)
11
Slow reactions
2MnO4(aq) + 5C2O42(aq) + 16H+(aq)
12
13
14
After corrosion
15
mol dm3
g
cm3 or dm3
atm
0.36 g
3
1
(a) Average rate
4.0 10 g s
90 s
17
360 cm
(b) Average rate
4.0 cm3 s 1
90 s
3
18
2.
(c)
0.030 mol
3
0.60
mol
dm
0.0500 dm3
2.
(d)
Rate of reaction
Rate of reaction
= 2
w.r.t. HCl(aq)
w.r.t. MgCl2(aq)
Increase in concentration of MgCl2(aq) in 90 s
1
0.60 mol dm 3 0.30 mol dm-3
2
20
2. Instantaneous rate
The rate at a particular instant of the
reaction is called the instantaneous rate.
For the chemical reaction
aA + bB cC + dD
Instantaneous rate
d[A] 1
d[B] 1
d[C] 1
d[D] 1
( )
( )
( )
( )
dt
a
dt b
dt c
dt d
[X] = molarity of X
21
2. Instantaneous rate
The rate at a particular instant of the
reaction is called the instantaneous rate.
For the chemical reaction
aA + bB cC + dD
Instantaneous rate
d[A] 1
d[B] 1
d[C] 1
d[D] 1
( )
( )
( )
( )
dt
a
dt b
dt c
dt d
Units : mol dm3 s1, mol dm3 min1, mol dm3 h1etc.
22
23
(reactant)
24
+ C
(product)
25
26
27
28
29
Concentration of product Z
(mol dm3)
Q.3
30
X + Y 2Z
C
B
A
Time of reaction (min)
Concentration of product Z
(mol dm3)
1 5.4 mol dm 3
Average rate
0.39 mol dm 3 min1
2
7 min
31
X + Y 2Z
C
B
A
Time of reaction (min)
Concentration of product Z
(mol dm3)
X + Y 2Z
32
C
B
Instantaneous rate at A
1 (6.0 - 0.0) mol dm3
2
(1.6 - 0.0) min
1.9 mol dm 3 min 1
1.6
Concentration of product Z
(mol dm3)
X + Y 2Z
33
5.1
B
2.7
Instantaneous rate at B
1 (5.1 - 2.7) mol dm 3
2
(3.0 - 1.0) min
0.6 mol dm 3 min 1
A
Time of reaction (min)
Concentration of product Z
(mol dm3)
X + Y 2Z
34
C
B
Instantaneous rate at C 0
A
Time of reaction (min)
35
1. Continuous measurements
Experiment is done in ONE take.
The reaction rates are determined by
measuring continuously a convenient property
which is directly proportional to the
concentration of any one reactant or product
of the reaction mixture.
36
Properties to be measured :
Gas volume / Gas pressure / Mass /
Color intensity / Electrical
conductivity
(3) 2H2O2(aq)
2H2O(l) + O2(g)
Temperature is
kept constant
38
39
dV
slope
rate
dt
Q.4
(2) Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
Rate
Rate
40
Sigmoid curve
42
stopwatch
cotton wool plug
limestone pieces
of known mass
measured volume of
standard
hydrochloric acid
electronic
balance
43
Loss of mass
(m)
dm
slope
rate
dt
time
mfinal - mt
45
mfinal = mfinal m0
( m0 = 0)
d[H ]
slope
= rate 2
dt
time
1.4 Colorimetry
colour intensity [coloured species]
d(colour intensity)
rate
dt
46
48
cuvettes
A colorimeter
49
Yellow
light
Yellow
filter
Blue solution
Complementary colours
50
Red Cyan
51
Red Cyan
Green Magenta
52
Red Cyan
Green Magenta
Blue Yellow
CMYK
Pairs of opposite colours are complementary
colours
53
I0
55
I0
I
100%
% transmittance
I0
56
I0
Absorbance log10
If I = I0 ,
If I = 0 ,
%T = 100%
%T = 0%
A = log101 = 0
A log10
zero absorption
complete absorption
A = bC
Beers law
57
Deviation at higher
concentrations
C
58
Q.5
[I2]
d[I2 ]
slope
rate
dt
time
A
dA
slope
rate
dt
59
time
60
61
d(PT )
rate
dt
PT = total pressure of the reaction
mixture
62
Q.6
(i) 2NO(g) + 2H2(g) N2(g) + 2H2O(g)
(ii) 3H2(g) + N2(g) 2NH3(g)
At fixed V and T, PT n
In both reactions,
n as the reactions proceed
PT as the reactions proceed
63
suction
flask
dilute hydrochloric acid
magnesium ribbon
pressure sensor
to data-logger
interface and computer
65
66
67
Experiment
[S2O32(aq)] / M
[H+(aq)] / M
1
2
3
0.10
0.08
0.04
1
1
1
0.02
68
yellow
precipitate
1
Average
rate
time taken to blot out the mark
73
dS
dt
S
slope average rate
t
amount of S
If S and t are small(early stage)
dS S
dt t
time
74
dS S
dt t
Since S is a constant
dS S 1
dt t t
75
S 1
Initial rate
t t
1
2
''
k [S2O3 (aq)]x
t
76
Expt.
77
[S2O32(aq)] [H+(aq)]
(M)
(M)
Time taken
(t)
to mask the
mark / s
0.10
10
0.08
13
0.04
25
0.02
50
1
t
/ s1
Q.7
1
t
1 ''
2
x
k [S2O3 (aq)]
t
Linear x = 1
[S2O32(aq)]
78
(excess)
(excess)
Halloween clock
80
(fixed)
Br2
(excess)
81
Br
3Br2
(fixed)
Br
82
83
84
Quenching methods:
Temperature
86
CH3COCH3 + I2
H+ as catalyst
CH3COCH2I + HI
Q.8
The reaction is quenched by adding to it NaHCO 3(aq)
that removes the catalyst.
HCO3(aq) + H+(aq) H2O(l) + CO2(g)
87
CH3COCH3 + I2
H+ as catalyst
CH3COCH2I + HI
Q.9
Titrated with standard solution of Na2S2O3(aq) using
starch as indicator (added when the end point is near)
88
CH3COCH3 + I2
H+ as catalyst
CH3COCH2I + HI
Q.10
The excess S2O32(aq) would react with H+ to give a
cloudy mixture with a pungent smell.
S2O32(aq) + 2H+(aq) S(s) + SO2(g) + H2O(l)
89
90
91
Factors
Affecting
Reaction Rates
92
Collision Theory
No reaction
Sufficient K.E.
Incorrect orientation
93
Collision Theory
No reaction
Correct orientation
Insufficient K.E.
94
Collision Theory
Sufficient K.E.
Correct orientation
Effective collision
95
Collision Theory
Activation energy
Collision Theory
Activation energy
Higher Ea
more K.E. required for effective collision
slower reaction
97
Collision Theory
Activation energy
Lower Ea
less K.E. required for effective collision
faster reaction
98
Collision Theory
Activation energy
100
particle size
size
particle
pressure
pressure
catalyst
catalyst
temperature
temperature
light
light
Effect of concentration
101
Effect of concentration
(a) 2.0
2.0 M
M HCl
HCl
(a)
(b) 1.0
1.0 M
M HCl
HCl
(b)
(c) 0.5
0.5 M
M HCl
HCl
(c)
Reaction rate:
rate:
Reaction
(a) >> (b)
(b) >> (c)
(c)
(a)
102
Effect of concentration
Time for
for reaction
reaction to
to
Time
complete: tt11 << tt22 << tt33
complete:
Higher [HCl(aq)]
[HCl(aq)]
Higher
Faster
Faster reaction
reaction
103
[X]
Reactant particles are more crowded
Collision frequency
Number of effective collisions
Reaction rate
104
aA + bB cC + dD
Rate k[A]x[B]y
where x and y are the orders of reaction
with respect to A and B
k is the rate constant
units mol dm3 s1/(mol dm3)x+y
105
aA + bB cC + dD
Rate k[A]x[B]y
x and y can be integers or fractional
x y is the overall order of reaction.
x, y can ONLY be determined experimentally.
106
Effect of pressure
Only applicable to reactions involving gaseous
reactants.
107
Pressure
Reactant particles are more crowded
Collision frequency
No. of effective collisions
Rate of reaction
108
Effect of temperature
Applicable to ALL reactions
109
T
K.E. of particles
Collision frequency (minor effect) and
No. of particles with K.E. > Ea (major effect)
No. of effective collisions
Rate of reaction
110
Rate
Rate of reaction
exponentially with temperature
Rate e
Ea
RT
In general, a 10oC in T
doubles the rate.
T / C
111
112
Rate involving
involving
Rate
powdered solid
solid
powdered
reactant is
is higher
higher
reactant
Reason: higher
higher
Reason:
chance of
of contact
contact
chance
between reactant
reactant
between
particles
particles
113
Q.11
0.5 g powder
0.5 g granule
114
Effect of Catalyst
A catalyst is a substance that alters the rate
of a chemical reaction by providing an
alternative reaction pathway with a different
activation energy.
A positive catalyst speeds up a reaction by
providing an alternative reaction pathway
with a lower Ea.
115
Effect of Catalyst
Catalysts remain chemically unchanged at the
end of reactions.
116
H2O2(aq)
MnO2 as catalyst
2H 2O(l) + O2(g)
Physical measurement
117
2H 2O(l) + O2(g)
H2O2(aq)
MnO2 as catalyst
118
MnO2 as catalyst
2H 2O(l) + O2(g)
Q.13
[H2O2
]
Without MnO2
With MnO2
time
120
Effect of light
Light with specific frequency (E h) can
provide sufficient energy to break a particular
chemical bond in a reactant leading to a
photochemical reaction.
Br Br
Br + Br
Autocatalysis
Catalysis in which the product acts as the
catalyst of the reaction
2MnO4(aq) + 16H+(aq) + 5C2O42(aq)
2Mn2+(aq) + 10CO2(g) + 8H2O(l)
CH3COCH3(aq) + I2(aq)
CH3COCH2I(aq) + H+(aq) + I(aq)
122
Q.14
[MnO4]
Rate
Sigmoid curve
Rate
123
time
The END
124
Back
Example 13-1A
0.18 g
(12.0 16.0 2) g mol - 1
= 0.0041 mol
0.0041 mol
Average rate =
60 s
= 6.83 105 mol s1
125
Answer
Example 13-1B
In the uncatalyzed decomposition of hydrogen p
eroxide solution into water and oxygen at room c
onditions, the volume of oxygen given out in 20 h
ours is 5 cm 3. What is its average rate in mol s 1 f
or that time interval?
2H 2O 2(l) 2H 2O(l) + O 2(g)
(Molar volume of gas at room temperature and p
ressure= 24.0 dm 3 mol 1)
Answer
126
Example 13-1B
Back
Number of moles of O2 =
5 cm 3
3
1
24
000
cm
mol
= 2.08 104 mol
127
Example 13-1C
The change in concentratio
n of reactant X in a chemic
al reaction is illustrated in
the graph on the right.
128
Example 13-1C
With the use of the graph, calculate
(a) the initial rate of the reaction;
(b) the average rate for the time
interval from
the 1st to the 2nd
minute;
(c) the instantaneous rate at the 3rd
minute.
1
(Give your answers in mol dm3 min
.)
Answer
129
Example 13-1C
(a) Initial rate
=
0.160)
mol
dm
=
(1.2 0) min
= -0.05 mol dm-3 min-1
130
Example 13-1C
(b) Average rate
(0.080 0.110) mol dm 3
=
(2 1) min
= -0.03 mol dm-3 min-1
131
Back
Example 13-1C
132
133
134
Answer
135
Initial rate
Back
-3
Back
Example 13-2
Hb4(CO)3
d [Hb 4 (CO)3 ]
1 d [Hb]
1 d [CO]
Rate
dt
4
dt
3
dt
137
Back
Rate =
138
2H2O(l)
d [O 2 ( g)]
1 d [H2 O(l)]
1 d [H2 (g)]
2
dt
2 dt
dt
Answer
Example 13-3A
Alkaline hydrolysis of ethyl ethanoate (an
ester) using sodium hydroxide solution is
represented by the following equation:
CH3CO2CH2CH3(l) + NaOH(aq)
CH3CO2Na(aq) + CH3CH2OH(aq)
Example 13-3A
(a) Suggest a method to quench the
reaction mixture so that the
concentration of sodium hydroxide
solution can be determined accurately.
Explain briefly why this method can
be
Answer
used.
(a) The reaction mixture can be quenched by pipetting a
sample of the reaction mixture into a conical flask
containing ice water. The cooling and dilution of the
reaction mixture decrease the reaction rate sufficiently for
chemical analysis.
140
Example 13-3A
(b) Explain why the change in concentration
of sodium hydroxide solution but not
that of ethyl ethanoate is measured in
order to determine the rate of the above
reaction.
Answer
(b) Sodium hydroxide is a strong alkali that reacts with strong
mineral acids almost instantaneously. Therefore, the
titration of sodium hydroxide solution and dilute
hydrochloric acid provides accurate experimental results.
141
Answer
Example 13-3A
10
8
10
10
Option B
Time after mixing
Volume of HCl
(min)
added at the end
point (cm3)
142
Example 13-3A
(c) Sodium hydroxide is a reactant of the hydrolysis. As the
reaction proceeds, the concentration of sodium hydroxide
in the reaction mixture decreases with time, and hence
the amount of dilute hydrochloric acid used in the titration.
Thus, option A is a reasonable set of experimental results.
143
Example 13-3A
(d) Name a suitable indicator for the
titration.
(d) Methyl orange / Phenophthalein
Back
144
Answer
Example 13-3B
A student recorded the following
experimental results for the reaction of zinc
and dilute hydrochloric acid.
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
Time
0. 1. 2. 3. 4. 5.0 6. 7. 8. 9.
(min)
0
0 0
0
0
0 0 0
0
Volume
of H2(g)
produce
d (cm3)
145
15 26 33 38
40
41 42 42 42
Example 13-3B
(a) Plot a graph of volume of hydrogen gas
produced against time.
(a)
146
Answer
Example 13-3B
(b) Describe the change in the rate of the
reaction using your graph in (a).
Answer
147
Example 13-3B
(c) Explain how you can measure the initial
rate of the reaction graphically.
Answer
148
Example 13-3B
Back
Answer
34)
cm
=
(8 2) min
= 2 cm3 min-1
149
Back
CH3COOCH2I(aq) + HI(aq)
Answer
Let's Think 1
Explain why sawdust burns explosively in pure
oxygen but slowly in air.
A higher concentration of oxygen increases
the rate of combustion.
Back
151
Answer
Answer
152
153
CaCl2(aq) + H2O(l) +