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Chemical Kinetics
Chemical Kinetics  Kinetics - study of rates of chemical
Rates of Chemical Reactions reactions and the mechanisms by which
they occur.
 Reaction rate - increase in
concentration of a product per unit time
or decrease in concentration of a reactant
per unit time.
 Reaction mechanism - the series of
molecular steps by which a reaction
occurs.

The Rate of Reaction

Kinetics versus Thermodynamics  Consider the hypothetical reaction,
 Thermodynamics determines if a reaction can occur. aA(aq) + bB(aq)  cC(aq) + dD(aq)
 Kinetics determines how quickly a reaction occurs.  equimolar amounts of reactants, A and B, will be
◦ Some reactions that are thermodynamically consumed while products, C and D, will be
feasible are kinetically so slow as to be formed as indicated in this graph:
imperceptible. 1.2
 [A] = concentration of A

Reactants & Products

1 in M ( mol/L).

Concentrations of
Cdiamond  O2g   CO2g  G o298  396 kJ 0.8
[A] & [B]  Reaction does not go
0.6
[C] & [D] entirely to completion.
VERY SLOW 0.4
◦ The [A] and [B] > 0
0.2 plus the [C] and [D]
H+aq  + OH-aq   H 2Ol  G o298 = -79 kJ 0
< 1.

INSTANTANEOUS
0
50

0
10

15

20

25

30

35
Time
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The Rate of Reaction C 4 H 9Cl(aq)  H 2 O ( l ) 

 C 4 H 9 OH(aq)  HCl(aq)

[C4H9Cl] plot of [C4H9Cl] vs t

aA(aq) + bB(aq)  cC(aq) + dD(aq) (M) Time, t (s)
0.12
0.1 0
0.0905 50 0.1

0.082 100
- Mathematically, the rate of a reaction can 0.0741 150
0.08

[C4H9Cl], M
be written as: 0.0671 200 0.06

- A  - B + C + D

0.0549 300 0.04
0.0448 400
Rate =  or  0.0368 500
0.02

a t b t c t d t 0.02 800 0
0 500 1000 1500 2000 2500
0.005 1500
In terms of In terms of Time, s

products 0.0025 2250

reactants

 Average rate of reaction – rate over a period of time  Instantaneous rate of reaction – rate at a
 C 4 H 9 Cl  particular time
Average Rate  
t
  Instantaneous rate at 0 s –
 
C H Cl   C 4 H 9 Cl initial time Initial Rate
   4 9 final time 
 
 final time  initial time  
 
[C4H9Cl] (M) Time, t (s) Average rate
0.1 0
0.0905 50 0.00019
0.082 100 0.00017
0.0741 150 0.000158
0.0671 200 0.00014
0.0549 300 0.000122
0.0448 400 0.000101
0.0368 500 0.00008
0.02 800 0.000056
0.005 1500 2.14286E-05
0.0025 2250 3.33333E-06
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 Instantaneous rate - slope (negative Rate Law Expressions / Rate Laws

for reactants, positive for products) of the  RATE LAW expression (or simply rate law)
tangent line passing through time t. ◦ Gives dependence of rate on concentration of species
◦ It is a derivative of the curve at that point.
1 C4 H9Cl Rate = k[reactant1]n[reactant2]m...
Rate = - x
1 t
◦ m, n  reaction orders (rate is nth order with
◦ INITIAL RATE respect to reactant 1, mth order wrt reactant 2)
 the instantaneous rate at t = 0 ◦ m + n  overall reaction order
 Important parameter being measured because it
gives a more accurate measure of rate ◦ k  rate constant – a very important rate parameter,
as it describes how the reaction proceeds
 Changes when the initial concentration of reactant
also changes

Determining Rate Laws  Consider the following rate for the

reaction:
 Consider the following data for the
NH 4(aq)  NO3(aq)
-

 2H 2O (l)  N 2(g)
decomposition of H2O2:
H2O2  H2O + ½O2 Experiment #
Initial [NH4+ ]
M
Initial [NO3- ] Observed Initial Rate,
M M/s
Observed Initial Rate, 1 0.01 0.2 5.4 x 10-7
Experiment # [H2O2] M 2 0.02 0.2 10.8 x 10-7
M/s 3 0.2 0.0202 21.6 x 10-7
1 0.01 5.4 x 10-7 4 0.2 0.0404 43.3 x 10-7
2 0.02 10.8 x 10-7
3 0.04 21.6 x 10-7 - as NH4+ doubles, the initial rate doubles!
- as NO3- doubles, the initial rate also doubles!
 What is the order with respect to H2O2?
 What is the rate law for the decomposition  Rate  [NH 4 ], [ NO 3- ]
process?
 Rate  k [NH 4 ][ NO3- ]
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The following data were obtained for the Types of reaction based on Rate
following reaction at 25oC. What is the rate Law Expressions
law expression for the reaction?
Possible
Order of Unit of k (when
Reaction Experimental
2 A(g) + B(g) + 2 C(g)  3 D(g) + 2 E(g) Rate Law
Reaction t in secs)

A  products Rate = k Zero order M/s

Initial rate of
Initial [A] Initial [B] Initial [C] formation of First order wrt
A  products Rate = k[A] [A], First order 1/s
Experiment (M) (M) (M) D (M/s) overall

1 0.20 0.10 0.10 2.0 x 10-4 2nd order wrt

A  products Rate = k[A]2 [A], 2nd order 1/M-s
2 0.20 0.30 0.20 6.0 x 10-4 overall
1st order wrt [A],
3 0.20 0.10 0.30 2.0 x 10-4 A + B  products Rate = k[A][B] 1st order wrt [B], 1/M-s
2nd order overall
4 0.60 0.30 0.40 1.8 x 10-3

Differential Rate Law Forms Integrated Rate Law Forms

Possible Experimental Differential Rate law Possible Experimental

Reaction Reaction Integrated Rate law form
Rate Law form Rate Law

A 
A  products Rate = k 
t
k A  products Rate = k A   A0 - k t
A 
A  products Rate = k[A]   k[A] A  products Rate = k[A] lnA    k t  lnA 0
t
A  1 1
A  products Rate = k[A]2   k[A]2 kt
t
A  products Rate = k[A]2
A A 0
A  B
A + B  products Rate = k[A][B]    k[A][B]
t t
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Integrated Rate Law Equations and

Determination of Reaction Orders
 Correlation with Linear Equation A   A0 - k t
y  mx  b lnA   k t  lnA 0
y  mx  b
 If you are determining the order of reaction 1 1
for a particular reactant and you have a set k t
of concentration-time data (3 data points is A A0
enough) wrt the reactant, then you can use
correlation with integrated rate laws.

 Concentration-versus-time data for the thermal Time

decomposition of ethyl bromide are given in the (min) 0 1 2 3 4 5
table below. Use the following graphs of the ln [C2H5Br] 0.00 -0.20 -0.40 -0.60 -0.80 -0.99
data to determine the rate of the reaction and
the value of the rate constant.
lnA    k t  lnA 0

C 2 H 5 Brg  
 C 2 H 4g   HBrg  at 700K
Time
Time (min) 0 1 2 3 4 5
(min) 0 1 2 3 4 5
1/[C2H5Br] 1.0 1.2 1.5 1.8 2.2 2.7
[C2H5Br] 1.00 0.82 0.67 0.55 0.45 0.37
1 1
A   A 0 - k t kt
A A 0
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[C2H5Br] vs. time

1.2
 Half-life of reactions, t1/2 – time when half of the initial
1 1/[C2H5Br] vs. time concentration of reactant is consumed.
0.8
[C 2 H 5 B r]

0.6 ◦ To obtain half-life equation, just substitute [A] = ½ [A]0 when

0.4
3
t = t1/2
0.2
0
2 1 1
0 1 2 3 4 5
kt

1 /[C 2 H 5 B r]
Time (min) A   A 0 - k t lnA    k t  lnA 0 A A0
1

ln [C2H5Br] vs. time 0

0 1 2 3 4 5
0
Time (min)
-0.2 0 1 2 3 4 5
[A]0 ln2 1
t1 
ln [C 2 H5 Br]

-0.4
t1  t1 
-0.6
-0.8 2 2k 2 k 2 kA 0
-1
-1.2
Time (min)

Sucrose, C12H22O11, which is commonly known as table sugar, reacts in

 Integrated Rate Law solution
dilute acid solutions to form two simpler sugars, glucose and fructose.
X 0 order Y 1st order Y 2nd order Y
C12 H22 O11(aq) + H2O(l)  2C6H12O6(aq)
Time (min) [C12H22O11], M ln[C12H22O11] 1/[C12H22O11]
At 23oC
and in 0.5M HCl, the following data were obtained for the 0 0.316 -1.152013065 3.164556962
disappearance of sucrose: 39 0.274 -1.294627173 3.649635036
80 0.238 -1.435484605 4.201680672
Time (min) [C12H22O11], M 140 0.19 -1.660731207 5.263157895
210 0.146 -1.924148657 6.849315068
0 0.316
R2 0.99004 0.99976 0.98474
39 0.274
80 0.238 1st order plot
0.35
0 order plot 2nd order plot
140 0.190 0 8
0.3 0 50 100 150 200 250
0 order plot 7
210 0.146 0.25 -0.5
6
2nd order plot
0.2 5
-1 1st order plot
0.15 4
(a) Determine the order of reaction and the rate law expression. -1.5 3
0.1 y = -0.00080x + 0.30816
(b) What is the half-life for the conversion of sucrose into glucose and 0.05 R² = 0.99004 -2 y = -0.00367x - 1.14882
2 y = 0.01753x + 2.98171
1
fructose based on the conditions of analysis? 0 R² = 0.98474
0 50 100 150 200 250 -2.5
R² = 0.99976 0
0 50 100 150 200 250
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 Log Rate solution

Rate Determination of Rate Laws
Time [C12H22O11], ∆[C12H22O11]/
∆[C12H22O11] ∆Time log(rate) log[C12H22O11]
(min) M ∆Time  Write the general form of the rate law
0
39
0.316
0.274 -0.042 39 0.001076923 -2.967815317 -0.562249437
expression (depends on the reactants
80 0.238 -0.036 41 0.000878049 -3.056481356 -0.623423043 present)
140 0.19 -0.048 60 0.0008 -3.096910013 -0.721246399  Determine the orders of reaction wrt
210 0.146 -0.044 70 0.000628571 -3.201645364 -0.835647144
each reactant
log rate method ◦ Log-rate ratio technique
-2.95
-0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0  Initial rates and initial concentrations of reactants
-3

log rate method -3.05

◦ integrated rate law technique
-3.1  Concentration-time data

y = 0.7968x - 2.5344
-3.15
 Determine the rate constant k
-3.2
R² = 0.9644
-3.25

Experimental Methods of Consider the gas-phase reaction between nitric oxide and bromine at 273 oC:

Determining Rate Law 2NO(g) + Br2(g)  2NOBr(g)

The following data for the time of appearance of NOBr were obtained:
 Initial Rates Method (Method of Initial
Experiment # [NO], M [Br2], M Time, sec
Rates) 1 0.11 0.25 41.67
◦ Initial rates of reaction are obtained 2 0.27 0.25 6.67

◦ Time involved not > 5 minutes from start of 3 0.12 0.50 16.71
4 0.36 0.50 1.36
reaction
◦ If time is given instead of rate, the rate can be (a) Determine the rate law
(b) Calculate the average value of the rate constant for the appearance of
is approximated by 1/t NOBr.
[concentration ] (c) How is the rate of appearance of NOBr related to the rate of
Rate  disappearance of Br2?
t
(d) What is the rate of disappearance on Br2 when [NO] =0.075 M and [Br2]
1 1 = 0.185 M?
 Rate  
t t
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Nature of Reactants
Factors That Affect Reaction Rates
 Chemical properties of reactant affect rates
 There are several factors that can
2 Na s   2 H 2 O    2 NaOH aq   H 2g 
influence the rate of a reaction:
Violent and rapid reaction - H 2 ignites and burns.

1. The nature of the reactants. Ca s   2 H 2 O    Ca OH 2 aq   H 2 g 

Slow reaction.
2. The concentration of the reactants.
Mg s   H 2 O    No reaction
3. The temperature of the reaction.
Not perceptible to human eye
4. The presence of a catalyst.
Acid-Base neutralizations, salt formation, and
precipitation reactions or ION-EXCHANGE reactions
are usually FASTER than reactions involving COVALENT-
bond breakage and formation.

Nature of Reactants
Concentration of reactants
 The Phase of reactants affect the rate of reaction
Rate  [reactant]
Mg s   H 2 O    No reaction - from Rate Law Expression
Not perceptible to human eye
 In the molecular level, increasing the
Mg (s)  H 2O ( g ) 
 MgO (s)  H 2 (g)
concentration of reactants means
Very fast process increasing the chances of reactant
 Homogenous reactions are faster than heterogenous reactions encounters, or COLLISIONS
◦ Basic idea of COLLISION THEORY of
 Heterogenous reactions with finely divided particles are usually
fast reactions
 Dissolution of “panutsa” versus plain “table sugar”.
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Collision Theory of Collision Theory of

Reaction Rates Reaction Rates
 Three basic events must happen for a  To increase chances/probability of collisions, Temperature
(since KE of particles as T increases)
reaction to occur. The atoms, molecules
or ions involved must:
1. Collide.
2. Collide with enough energy to break
and form bonds.  Also, T allows initial energy for bond breakage of reactant
3. Collide with the proper orientation for a molecules.
reaction to occur.
CH 4(g)  O 2(g) (no heat added, no reaction)
,
CH 4(g)  O 2(g) matches
   CO 2(g)  H 2 O (g)  891 kJ

Collision Theory of 2H 2(g)  O 2 ( g ) 

 2H 2O(g)
Reaction Rates
 Proper orientation of particles (upon collision) is also
necessary for formation of products to occur.

2H 2(g)  O 2 ( g ) 
 2H 2O (g)
H 2(g)  I 2 ( g ) 
 2HI (g)
◦ will product form in the following orientation of
molecules?
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• Collision Theory only explains that successful Transition State Theory

formation of products happens when
– KE energy sufficient to form and break the
chemical bonds
– correct orientation of molecules is achieved upon
collision
 Transition state theory postulates that reactants
form a high energy intermediate, the transition
state, which then falls apart into the products.

 For a reaction to occur, the reactants must

• It gives an incomplete description of the
acquire sufficient energy to form the transition
corresponding energy involved in the
state.
rearrangement of atoms to form the final
◦ This energy is called the activation energy or Ea.
compound

H 2(g)  I 2( g ) 
 2HI (g)
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Dependence of Rate on Temperature -E a

k = Ae RT
– Arrhenius Equation
k  rate constant
 Svante Arrhenius developed this A  frequency factor
relationship among E a  Activation energy
◦ (1) the temperature (T) joule
◦ (2) the activation energy (Ea), and R  gas constant 8.314
mole - K
◦ (3) the specific rate constant (k). T  Temperature in K
-E a
k = Ae RT

or
Ea
ln k = ln A -
RT

The Arrhenius Equation The Arrhenius Equation

Subtract one equation from the other.
 If the Arrhenius equation is written for two Ea  Ea 
temperatures, T2 and T1 with T2 >T1. ln k 2  ln k1  ln A - ln A -   
RT2  RT1 
Ea ln k 2  ln k1 
Ea Ea
ln k1  ln A - -
RT1 RT2
RT1
k 2 Ea  1 1 
and ln
k1
   
R  T1 T2 
Ea or
ln k 2  ln A - k 2 Ea  T2 - T1 
RT2 ln   
43
k1 R  T2 T1 
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The temperature dependence of the rate constant for Factors That Affect Reaction Rates
the reaction

CO(g) + NO2(g)  CO2(g) + NO(g)

 The presence of a catalyst.
◦ May be included in the actual reaction, but is not
is tabulated below. Calculate Ea and A. consumed in the process.
◦ Catalysts change reaction rates by providing an
Temperature, K k, M-1 s-1 alternative reaction pathway with a lower Ea
600 0.028
650 0.22
700 1.3
750 6.0
800 23

Presence of Catalysts
Presence of Catalysts
 Homogeneous catalysts exist in same phase as
the reactants. N 2g   3 H 2g  Fe
or  2 NH 3g 
Fe 2 O 3

 Heterogeneous catalysts exist in different

phases than the reactants. Haber Process
◦ Catalysts are often solids.

2 SO 2 g   O 2g  V   2 SO 3 g 

2 O 5 or NiO/Pt
C8 H18g  + 25 O 2 g   16CO 2g   18 H 2 Og 
NiO and Pt

2 CO g  + O 2g  NiO
  2 CO 2 g 
and Pt Sulfuric acid preparation

2 NO g  NiO
  N 2 g   O 2g 
and Pt