Summary of Integrated Rate Laws for aA + bB  Prods.

Differential Conditions Integral Rate Equation Half-Life, t½

Order Rate Eqn.
0 R=k - [A] – [A]0 = – kt [A]0/(2k)
½ R = k[A]1/2 - [A]½ – [A]0½ = – ½kt ?
1 R = k[A] - ℓn([A]/[A]0) = – kt ℓn2/k
3/
2 R = k[A]3/2 - [A]–½–[A]0–½ = ½kt ?
2 R = k[A]2 - [A]–1 – [A]0–1 = kt 1/([A]0k)
3 R = k[A]3 - [A]–2 – [A]0–2 = 2kt 3/(2[A]02k)
R = k[A][B] [B]0/[A]0 = b/a –1 – [A] –1 = k(b/a)t
[A]
= k(b/a)[A]2  [B]/[A] = b/a 0

R = k[A][B] [B]0/[A]0  b/a ℓn([A]/[B]) = (b[A]0–a[B]0)k · t + ln([A]0/[B]0)

2
For A  C,  [C] 
 0    k [A]0  [C]0 t
[A]
R = k[A][C] n
C=autocatalyst:  [A]0  [C]0  [A] [A]0 

For A + 2B 
3 R = k[A][B]2 P, x=[P]:
2x 1 [A]0 [B]0  2 x 
 n  kt
2[A]0  [B]0 [B]0  2x[B]0 2[A]0  [B]0 2
[B]0 [A]0  x 
1 © Prof. Zvi C. Koren 20.07.2010
 Examples of Different Kinetic Order Reactions
0th order
2NH3(g)  N2(g) + 3H2(g)

Rate Equation : R NH3  k

k = 1.5 x10-3 M/sec

Nike Problem: Just Do It!

2 © Prof. Zvi C. Koren 20.07.2010

Examples of Different Kinetic Order Reactions (cont’d)
1st order
2H2O2(g)  2H2O(g) + O2(g)

Rate Equation:
R = k[H2O2]

3 © Prof. Zvi C. Koren 20.07.2010

 1st Order Example
Hydrolysis of triphenylmethyl chloride: Kinetic Data for the
Hydrolysis of TPM chloride
Ph3CCl + H2O  Ph3COH + H+ + Cl– Concentrations/M
Time/s
Experiments have shown that 103[H+] 103[Ph3CCl]
Rate Law: Rrxn = k[Ph3CCl] 0 - 1.44
18 0.104 1.336
How?
57 0.312
Follow rxn by:
a) titration of the liberated acid; 93 0.484
b) monitoring via pH meter. 171 0.757
A plot of ln[Ph3CCl] vs. t shows that rxn. is 1st order.
298 1.04
Results: 448 1.23
508 1.28
k = 4.34 x 10–3 s–1, t½ = 160 s
1800
1.44 -
DO IT, OF COURSE! (““)
Assume 100% reaction
4 © Prof. Zvi C. Koren 20.07.2010
Examples of Different Kinetic Order Reactions (cont’d)
2nd order
2HI(g)  H2(g) + I2(g)

Rate Equation:
R = k[HI]2

5 © Prof. Zvi C. Koren 20.07.2010

 Determination of Kinetic Order of Rxn. (3)
Fractional Lifetime Methods for Decomposition Reactions

Fractional lifetimes: t1/2, t3/4, …

[A]t 
1
t1/2  time for half to react (and half to remain)  “half-life”: 2
[A]0
1/2


1
t3/4  time for ¾ to react (and ¼ to remain)  “quarter-life”: [A]t
4
[A]0
3/4

Fractional lifetime ratios:

For example, t3/4/t1/2 1.5 2 3 5
Check it & Continue it!
Order 0th 1st 2nd 3rd

 Experimental fractional lifetime ratios can determine the reaction order

6 © Prof. Zvi C. Koren 20.07.2010

 Unusual 1st Order Reactions
Pseudo 1st Order Rxns and “Flooding”
Consider the rxn: aA + bB + cC  Products
and suppose that R = krxn[A][B]2[C]3
If we’re only interested in R w.r.t. A. then we can flood the rxn with B & C:
If [B]0, [C]0 >> [A]0, by a factor of at least 10, then [B], [C]  constant

R  k′[A], k′  k[B]2[C]3,
where k′ is known as the effective, apparent, or observed rate constant.
Kinetics are thus 1st order w.r.t. A, with these concentrations, and we can use the
logarithmic plot to evaluate k′:
n[A]  - k' t  n[A]0
krxn can be calculated from k′  krxn[B]2[C]3, by using the average values of [B] and
[C] over the run.
For example, if [B]0, [C]0 = 10[A]0 , and if the stoichiometry is 1:1:1, then
[B] = 0.9[B]0 & [C] = 0.9[C]0. Therefore,
[B]av = 0.95[B]0 & [C]av = 0.95[C]0.
7 © Prof. Zvi C. Koren 20.07.2010
 Apparent Rate Constants
From before,
[H+]
Example 3. Rxn.: CrCl2+  Cr3+ + Cl– +
 k 
Rate Law: Rrxn   k1  2  [CrCl2]  kapp[CrCl2]
 [H ] 
Note: The apparent order w.r.t. [H+] varies with [H+], i.e., pH:
For very basic solutions, high pH, low [H+]:
[CrCl2]
k2/[H+] >> k1  Rrxn  k2
[H]
Order of rxn. w.r.t. [CrCl2+] = 1
Order of rxn. w.r.t. [H+] = –1

For very acidic solutions, low pH, high [H+]:

k1 >> k2/[H+]  R rxn  k1[CrCl 2]
Order of rxn. w.r.t. [CrCl2+] = 1
Order of rxn. w.r.t. [H+] = 0
So, as stated, the apparent order w.r.t. [H+] varies with [H+].
8 (continued) © Prof. Zvi C. Koren 20.07.2010
 (continued)
From before, for the rxn.:

[H+]
Rxn.: CrCl2+  Cr3+ + Cl– +
d[CrCl2 ]  k2 
Rate Law:   R rxn   k1    [CrCl 2 ]

dt  [H ] 
k
kapp  k1  2
[H ]
Rearranging:
1 2
2
[CrCl ]
d[CrCl ]
dn[CrCl2 ]  k 2[H ]1, low [H ]
    k app
dt dt  k1[H ]0 , high [H ]

normalized rate
Order of rxn. w.r.t. [H+] varies from –1 to 0:
Plot of log(normalized rate) vs. log[H+] or pH would be interesting.

9 (continued) © Prof. Zvi C. Koren 20.07.2010

From
dn[CrCl 2 ]  k 2[H ]1, low [H ]
before:
normalized rate:   k app
dt  k1[H ]0 , high [H ]
log(k2) – 1·log[H+], low [H+]
log(normalized rate) 
log(k1) + 0·log[H+], high [H+]

Exact order of rxn w.r.t. [H+] can be determined.

Log (normalized rate)

slope = –1

slope = 0

Log ([H+])
10 (continued) © Prof. Zvi C. Koren 20.07.2010
 (continued)
Determination of rate constants:

dn[CrCl 2 ]
normalized rate    k app
dt
k2
kapp  k1  
[H ]

kapp
slope = k2

y-intercept = k1

[H+]–1
11 © Prof. Zvi C. Koren 20.07.2010