EXPERIMENT 1.

CHEMICAL KINETIC: DETERMINE REACTION ORDER

Determine reaction order of the reaction of FeCl3 and KI:

1
Fe3++ I- = Fe2++ I2 (1)
2

1. Principal
At a constant temperature, assume that there is a reaction written as follows:

A + B + ….  X + Y + …
and that the reaction follows a rate law of the form:
d  A d X 
 k . A . B 
n1 n2
v 
dt dt
We can determine the reaction rate of reaction (1) as:

d  Fe3  d  Fe2  n1 n2
v   k .  Fe3  .  I  
dt dt

When dt 0, the reaction rate is the initial rate, can generally be expressed as:

 d  Fe 2  
     k .  Fe3  n1 .  I   n 2
 0  0 (2)
 dt 
 t  0
Where:
 Fe3  and  I   : initial concentration of Fe3+ and I-
0 0

n1, n2: the order of the reaction with respect to Fe3+ and I-.
Therefore, taking logarithm of both sides of the equation (2) gives:
 d  Fe2  
ln      ln k  n .ln  Fe3   n .ln  I   (3)
 0 2  0
 dt  1
 t  0
When the initial concentration of ion I- is constant, equation (3) can be written as:
 d  Fe2  
ln      n .ln  Fe3   A (Where A = lnk + n ln[I-] = const)
 0 2 0 (4)
 dt  1
 t  0
when the initial concentration of Fe3+ is varied in a series of experiments, it is possible
 d  Fe 2  
to determine n1 by drawing a plot of ln     versus ln  Fe3  . The plot is a straight
 0
 dt 
 t  0

1
line with a slope of n1.
Similarly, when the initial concentration of Fe3+ is kept constant, equation (3) can be
written as:
 d  Fe 2  
ln      n .ln  I    B (Where B = lnk + n ln[Fe3+] = const)
 0 1 0 (5)
 dt  1
 t  0
when the initial concentration of I- is varied in a series of experiments, it is possible to
 d  Fe 2  
determine n2 by drawing a plot of ln     versus ln  I   . The plot is a straight line
 0
 dt 
 t  0
with a slope of n2.
The overall order of the reaction is: n = n1+ n2.
1 1
The initial rates are determined from the plot  f   . The plot is a straight line
 Fe 
2
t 
with a value of (slope)-1 being the initial rate. (That means: with each initial concentration
of Fe3+, we can determine one value of initial rate).
Determine the concentration of Fe2+
The concentration of Fe2+ is increasing with time and can be determined from the
concentration of I2.
The I2 concentration formation is determined by adding to the reaction mixture a
known volume of Na2S2O3 solution (with 5 drops of starch solution 1% as indicator). When
all Na2S2O3 react with formed I2 in the reaction, newly formed I2 will form a "blue-black"
colour complex with starch (from colourless to blue-black). Fe2+ concentration [Fe2+] = [I2]
= Cx can be calculated by:
N Na2 S2O3 .VNa2 S2O3  Cx .Vhhpu

Where:
N Na2 S2O3 ,VNa2 S2O3 : Normal of Na2 S2 O3 (0,02N) and total volume of Na2 S2 O3 solution
added (From the first time to time t).
Cx: Normal of Fe2+ at time t
Vx: Volume of reaction mixture.
2. Required materials
- 25mL buret, 50mL beaker,100mL beaker, 250mL beaker, 250mL erlenmeyer flask
- Solution of KI N/40, FeCl3 N/60, KCl 0,1N; HCl 0,1N; Na2 S2O3 0,02N; starch 1%.

2
3. Experiment
a. A series of experiment 1: Determine the order of the reaction with respect to Fe3+
Add chemicals to 4 different 250mL erlenmeyer flasks as shown in the following table:
Solution (mL) Trial 1 Trial 2 Trial 3 Trial 4
FeCl3 N/60 20 25 30 35
HCl 0,1M 10 10 10 10
KCl 0,1M 45 37,5 30 22,5
H2 O 5 7,5 10 12,5
Trial 1:
- Add 5 drops of starch solution 1% and 20 ml of KI N/40 solution to 250mL
erlenmeyer flask, record time to of reaction. Add V1 (mL) of Na2S2O3 0,02N
solution to reaction mixture. (Students should add V1 (mL) of Na2S2O3 0,02N before
adding KI N/40 solution).
- When the reaction mixture turn “blue-black”, record time t1 (when formed I2 reacts
with V1 mL Na2S2O3 0,02N solution added).
- Add V2 mL Na2 S2O3 0,02N solution to reaction mixture, record time t2 when
reaction mixture turn “blue-black” again.
- Continue the experiment to take 8 values of Vt – tt.
Repeat the experiment with erlenmeyer flask 2, 3, 4 as with the first trial.
Write down the results in the table:

Trial 1, [Fe3+]o= Trial 2, [Fe3+]o= Trial 3, [Fe3+]o= Trial 4, [Fe3+]o=

No VNa2S3O3 t (s) VNa2S3O3 t (s) VNa2S3O3 t (s) VNa2S3O3 t (s)
(mL) (mL) (mL) (mL)
1
2
3
4
5
6
7
8

b. A series of experiment 2: Determine the order of the reaction with respect to I-

Add chemicals to 4 different 250mL erlenmeyer flasks as shown in the following table:
Solution (mL) Trial 1 Trial 2 Trial 3 Trial 4
KI N/40 20 25 30 35
HCl 0,1M 10 10 10 10
KCl 0,1M 17,5 16 15 13,5
H2 O 32,5 29 25 21,5

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 Trial 1:
- Add 5 drops of starch solution 1% and 20mL of FeCl3 N/60 solution to 250mL
erlenmeyer flask, shake well, record time to of reaction.
- Next steps: conduct similar to the steps in series of experiment 1.
Write down the results of series of experiment 2 in the table:

Trial 1, [I-]o = Trial 2, [I-]o = Trial 3, [I-]o = Trial 4, [I-]o =

No VNa2S3O3 tpư (s) VNa2S3O3 tpư (s) VNa2S3O3 tpư (s) VNa2S3O3 tpư (s)
(mL) (mL) (mL) (mL)
1
2
3
4
5
6
7
8
4. Report
Calculate the results and write down in the following tables:
a. Series of experiment 1: Trial ............; [Fe3+]o=.........
1 1
Time (second) VNa2S2O3 (mL)  Fe 2  = Cx
CX t
….. ….. ….. ….. …..

1 1
Draw the plot  f   , determine the slope (a), then determine initial rate (1/a)
 Fe2  t 
of the reaction respectively to initial concentration of Fe3+.
 d  Fe2  
Draw the plot ln(1/a) = ln  
 dt  0 
   f ln  Fe3  , determine n .
 1
 t  0
b. Series of experiment 2: Trial............; [I-] =……….
1 1
Conduct similar to the above, draw the plot  f   , determine the slope (a),
 Fe 
2
t 
then determine initial rate (1/a) of the reaction respectively to initial concentration of I-.
 d  Fe2  
Draw the plot ln(1/a) = ln  
 dt   0  
   f ln  I   , determine n .
2
 t  0
The overall order of the reaction: n = n1 + n2.