Half-Life t1/2

Overall Order of Irreversible

Reactions from the Half-Life t1/2
 Batch Reactor Data
• Experimental technique: Method of Half
Lives
• Half life is the time required for
concentration of the reactant to fall to half
of its initial value.
• By determining half life as a function of
initial concentration, order and specific
rate can be determined.
Defining the half-life of the reaction, t1/2 , as the time needed for the
concentration of reactants to drop to one-half the original value, we obtain

This expression shows that a plot of log t1/2 vs. log CAo gives a straight line of
slope 1 - n, as shown in Fig. 3.5.
The half-life method requires making a series of runs, each at a different initial
concentration, and shows that the fractional conversion in a given time rises
with increased concentration for orders greater than one, drops with
increased concentration for orders less than one, and
is independent of initial concentratio for reactions of first order.
 Batch Reactor Data
• Experimental technique: Method of Half Lives
A  products
1  1 1 
t   1   1 
 rA  kC A k   1  C A C Ao 

dC A 1   C Ao 
 1

  kC A t   1    1
dt kC Ao    1  C A  

 Batch Reactor Data
• Experimental technique: Method of Half Lives
A  products t  t½
t½ 
2 1  1
C A  ½C Ao k   1 C Ao1
 rA  kC A

 1   C Ao 
 1

2 1 1
ln t ½  ln     1 ln C Ao t   1    1
k    1 kC Ao    1  C A  


obtain order from slope

obtain k from intercept after obtaining 
 @ t = t1/2  NA = ½ NA0
Half-lives Method @ V = V0  CA = ½ CA0

1 / 2CA 0 t1 / 2
dC A
  k  C A   C A   dC A  k  dt   C 
 A  dC A  k   dt
dt CA 0 0

1 1 / 2CA 0
CA 1 / 2  C A0  1  C A01
   k  ( t1 / 2  0)   k  t1/ 2
  1   1
CA 0

17

2  1  C A 01  C A 01
 k  t 1/ 2 

2  1  1  C A 01 
 k  t1/ 2
15
 1  1
13

2  1  1
ln t1/2

 C A 01  t 1 / 2 
11

9 k     1
7
 2  1  1 
ln t 1 / 2  ln    (1  )  ln C A 0
 k     1 
5
200 250 300 350
8

ln CA0
 Method of Half Lives Example
• Nitrogen oxide is a pollutant in automobile exhaust that can react with
oxygen to form nitrogen dioxide:

2NO  O2 
 2NO2 k2

• At 298 K the specific reaction rate is: k 2  1.4  10 9 ppm 2 min

Find t½ of 3000 ppm NO (typical pre-control exhaust level) in air?

What is t½ of 1 ppm NO (a typical polluted atmosphere value)?
since oxygen is highly in excess,

 rNO  kCNO CO  k 2CNO

 Method of Half Lives Example
• Nitrogen oxide is a pollutant in automobile exhaust that can react with oxygen to
form nitrogen dioxide:
2NO  O2 
 2NO2 k2

• At 298 K the specific reaction rate is: k 2  1.4  10 9 ppm 2 min

Find t½ of 3000 ppm NO (typical pre-control exhaust level) in air?

What is t½ of 1 ppm NO (a typical polluted atmosphere value)?

units on specific reaction rate imply  = 3

  
 rNO  kCNOC O  k 2CNO  k 2CNO
3
 Method of Half Lives Example
• Nitrogen oxide is a pollutant in automobile exhaust that can react with
oxygen to form nitrogen dioxide:

2NO  O2 
 2NO2 k2

• At 298 K the specific reaction rate is: k 2  1.4  10 9 ppm 2 min

Find t½ of 3000 ppm NO (typical pre-control exhaust level) in air?

What is t½ of 1 ppm NO (a typical polluted atmosphere value)?

substituting  = 3 into half-life expression:

2 1  1 231  1 3
t½   
k   1 C Ao
 1
k 3  1 C Ao
31
 
2.8  10 9 C2Ao
 Method of Half Lives Example
• Nitrogen oxide is a pollutant in automobile exhaust that can react with
oxygen to form nitrogen dioxide:

2NO  O2 
 2NO2 k2

• At 298 K the specific reaction rate is: k 2  1.4  10 9 ppm 2 min

Find t½ of 3000 ppm NO (typical pre-control exhaust level) in air?

What is t½ of 1 ppm NO (a typical polluted atmosphere value)?

substituting CNO = 3000 ppm: substituting CNO = 1 ppm:

3 3
t½   119.1 min t½    9
2.8  10  3000
9 2
 
2.8  10  1
9 2
1.071 10 min
 L3-8 Half-lives Method
Find the overall order of the reaction:
2 H2 + 2 NO  N2 + 2 H2O
From the following constant-volume data using
equimolar amounts of hydrogen and nitric oxide:

Initial Total Pressure, mmHg 200 240 280 320 360

Half-life, sec 265 186 115 104 67

13
 U2-Half-lives Method

The thermal decomposition of nitrous oxide

(N2O) in the gas phase at 1030 K is studied
in a constant-volume vessel at various
initial pressures of N2O. The half-life data
so obtained are as follows:
p0, mmHg 52,5 139 290 360
t½ , s 860 470 255 212

Determine a rate equation that fits these data

14
 L3-29 Half-lives Method
Determine the complete rate equation in units
of moles, liters, and seconds for the thermal
decomposition of tetrahydrofuran from the
half-life data in Table P29

o
Initial Total Pressure, mmHg Half-life, sec Temp. C
214 14.5 569
204 67 530
280 17.3 560
130 39 550
206 47 539
15