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Experiment 2K3

Name: Inkiru Bernard


ID#: 620022618
Lab Day: Friday

Abstract : The effect of ionic strength on the second order rate constant for the reaction of
malachite green and hydroxide ion was carried out at 302K. The second order rate constant for
the reaction at zero ionic strength was 34.51 5.41 dm3/mol/s and the slope of the plot was
1.7629 0.876.

Introduction : During this reaction, the effect of ionic strength on the rate constant for the
reaction of malachite green and hydroxide ion from which a carbinol is formed. The
experimentally determined rate law for this reaction is give by : -d[Dye]/dt = k1[Dye][OH-],
where k1 is the second order rate law. Since the initial concentration is much larger than that that
of malachite green, the rate law is simplified to : -d[Dye]/dt = k[Dye]; where k is the pseudofirst-order rate constant and is related to k1 by the equation k=k1[OH-]. When this equation is
integrated and rearranged to yield:
ln [Dye]- ln[ Dye] = -kt. The ions in solution are in equilibrium with in an activated complex
M# from which the product is formed. The ionic strength of a solution is given by the equation:
I= cizi2 where c is the concentration and z is the charge of the ith ion respectively. The
Debye-Huckel limiting law yields a relationship between the activity coefficient and the ion
strength of a species. In dilute aqueous solutions, at 298K, the relationship is given by log k1 =
log k01 + 1.018 zAaB I/(1 + I). This equation indicates that a linear plot of log k1 against
I/(1 + I) should yield a linear plot with a slope of 1.018 and an intercept of log k01. The
kinetics of the reaction will be studied by monitoring the absorbance of the solution with a
spectrophotometer over time. The absorbance of a solution containing several non-interacting
species is the sum of the absorbance of the individual species. The reaction will be studied at
613.07nm where the malachite green has a significant absorption coefficient. The absorption of
the reaction mixture at times t and 0 is given by At = l[Dye]t and A0 = l[Dye]0 which yields the
linear equation :
ln At ln A0 = -kt.
Procedure: 20 cm3 of malachite green was pipetted into five clean 100cm3 flasks. 40, 25, 10, 5
and 0 cm3 of potassium nitrate was added to the five flasks respectively. Distilled water was
added to yield a volume of about 80cm3 in each flask, the solutions were then mixed. The
wavelength of the spectrophotometer was set to 613,07 nm and the instrument zeroed with
distilled water. 5cm3 of NaOH was pipetted into flask 1 and the stopwatch started when half the
reagent was added. The volume of the flask was quickly adjusted up to the mark, thoroughly
mixed and a small volume transferred to a cuvette. The absorbance over time was measured at 30
second intervals for 5 minutes and then at 1 minute intervals until the absorbance reading had
levelled off. The temperature of the solution was then taken. The procedure was repeated for
flasks 2, 3, 4 and 5.

Results:
Table 1 : Table showing results of Run 1 for Flask 1
Absorbanc Time/m Ln
e
in
Absornace
0.04
0.5
3.21887582
5
0.037
1
3.29683736
6
0.036
1.5
3.32423634
1
0.033
2
3.41124771
8
0.032
2.5
3.44201937
6
0.03
3
3.50655789
7
0.029
3.5
3.54045944
9
0.027
4
3.61191841
3
0.026
4.5
3.64965874
1
0.025
5
3.68887945
4
0.023
6
3.77226106
3
0.022
7
3.81671282
6
0.019
8 -3.9633163
0.019
9 -3.9633163
0.017
10
4.07454193
5

0.017

11

0.015

12

0.015

13

0.013

14

0.013

15

0.012

16

0.01

17

0.01

18

0.01

19

4.07454193
5
4.19970507
8
4.19970507
8
4.34280592
2
4.34280592
2
4.42284862
9
4.60517018
6
4.60517018
6
4.60517018
6

Table 2: Table showing Results of Run 2 for


Flask 2
Absorbance
0.06
0.056
0.055
0.049
0.046
0.045
0.043
0.041
0.04
0.037
0.035
0.032
0.03
0.028
0.026
0.024
0.022
0.021
0.021
0.019
0.019
0.018
0.018
0.017
0.017
0.017

Time/min
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21

Ln
Absorbance
-2.81341
-2.8824
-2.90042
-3.01593
-3.07911
-3.10109
-3.14656
-3.19418
-3.21888
-3.29684
-3.35241
-3.44202
-3.50656
-3.57555
-3.64966
-3.7297
-3.81671
-3.86323
-3.86323
-3.96332
-3.96332
-4.01738
-4.01738
-4.07454
-4.07454
-4.07454

Table 3: Table showing Results of Run 3 for


Flask 3
Absorbance

0.058
0.056
0.054
0.051
0.049
0.046
0.044
0.043
0.042
0.04
0.034
0.033
0.032
0.029
0.028
0.025
0.024
0.023
0.021
0.021
0.021

Time/min

0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
6
7
8
9
10
11
12
13
14
15
16

Ln
Absorbanc
e
-2.84731
-2.8824
-2.91877
-2.97593
-3.01593
-3.07911
-3.12357
-3.14656
-3.17009
-3.21888
-3.38139
-3.41125
-3.44202
-3.54046
-3.57555
-3.68888
-3.7297
-3.77226
-3.86323
-3.86323
-3.86323

Table 4: Table showing Results for Run 4


for Flask 4
Absorbanc
e

Time/mi
n

0.06

0.5

0.058

0.055

1.5

0.053

0.05

2.5

0.049

0.047

3.5

0.044

0.042

4.5

0.04

0.037

0.034

0.032

0.03

0.029

10

0.025

11

0.024
0.024
0.024
0.024

12
13
14
15

Ln
Absorba
nce
2.81341
2.84731
2.90042
2.93746
2.99573
3.01593
3.05761
3.12357
3.17009
3.21888
3.29684
3.38139
3.44202
3.50656
3.54046
3.68888
-3.7297
-3.7297
-3.7297
-3.7297

Table 5: Table showing Results for Run 5


for Flask 5
Absorbance

Time/
min

0.068

0.5

0.067

0.064

1.5

0.062

0.06

2.5

0.058

0.057
0.056
0.053

3.5
4
4.5

0.052

0.051

0.049

0.049

0.047

0.044

10

ln
Absorba
nce
2.68825
2.70306
2.74887
2.78062
2.81341
2.84731
-2.8647
-2.8824
2.93746
2.95651
2.97593
3.01593
3.01593
3.05761
3.12357

0.043

11

0.041

12

0.04

13

0.039

14

0.038

15

0.037

16

0.037

17

0.034

18

0.036

19

0.036

20

0.036

21

0.036

22

0.034

23

0.034

24

0.034

25

3.14656
3.19418
3.21888
3.24419
3.27017
3.29684
3.29684
3.38139
3.32424
3.32424
3.32424
3.32424
3.38139
3.38139
3.38139

Graphs
Graph 1: Graph showing ln(Absorbance) against Time/min for
Time/min
Flask 1

-0.5

10

15

20

y = -0.0745x - 3.2746
R = 0.9877

-1

ln(Absorbance)

-1.5
-2

-2.5
-3

-3.5
-4
-4.5
-5

Graph 2: Graph showing ln(Absorbance) against Time/min


for Flask 2
Time/min

0
0

10

15

20

-0.5
-1
ln(Absorbance)

-1.5
-2

-2.5
-3

-3.5
-4
-4.5

y = -0.0637x - 2.9278
R = 0.9596

25

Graph 3: Graph showing ln(Absorbance) against Time/min for


Flask 3
Time/min

0
-0.5

10

12

14

-1

16
18
y = -0.0703x - 2.8607
R = 0.9812

ln(Absorbance)

-1.5
-2

-2.5
-3

-3.5
-4
-4.5

Graph 4: Graph showing ln(Absorbance) against Time/min for


Time/min
Flask 4

0
0

10

12

14

-0.5
-1

TIme/min

-1.5
-2

-2.5
-3
-3.5
-4
-4.5

y = -0.0699x - 2.8295
R = 0.9693

16

Graph 5: Graph showing ln (Absorbance) against Time/min for Flask 5


Time/min

0
0

-0.5

ln(Absorbance)

-1
-1.5
-2

-2.5
-3
-3.5
-4

Calculations
To calculate [NaOH] in a flask:
0.02 mol .. 1000cm3
x mol .. 5 cm 3
x = 0.0001 mol
And if 0.0001 mol in 100cm3
x .. in 1000cm3
x = 0.001 mol/dm3
To calculate [KNO3] in a flask
0.2 mol in 1000cm3
x mol in

40 cm3

x = 0. 008 mol
And if 0.008 mol in 100cm3
x in 1000cm3
x = 0.08 mol/dm3

10

15

20

25

30

To calculate I using the formula : I= cizi2


I = 0.5 (0.001 x 12 + 0.001 x -12 + 0.08 x 12 + 0.08 x -12 )
I = 0.081 mol/dm3

Therefore I = (0.081) = 0.284


And I/(1 + I) = 0.222

To calculate k1 , we use to formula k1 = k/[OH-] where k is the slope from the plot of
ln(Absorbance) against Time/min
For Solution 1 = k1 = 0.0745/0.001 = 74.5 dm3/mol/s
Table 6: Table showing calculated graph parameters
[NaOH]

[KNO3]

I 1/2

0.001

0.08

0.162

0.081

0.001

0.05

0.102

0.051

0.001

0.02

0.042

0.021

0.001

0.01

0.022

0.011

0.001

0.002

0.001

I 1/2 / (1+ I1/2) k

0.28460
5
0.22583
2
0.14491
4
0.10488
1
0.03162
3

k1

0.221550587

0.0745

74.5

0.184227393

0.0637

63.7

0.126571775

0.0703

70.3

0.09492506

0.0699

69.9

0.03065343

0.0286

28.6

Graph 6: Graph Showing log(k1) against I1/2/(1 + I 1/2)


2.5

Log(k1)

1.5
y = 1.7629x + 1.5328

0.5

0
0

0.05

0.1

0.15

log k1

0.2

I1/2/(1 + I 1/2)

0.25

1.87215
6
1.80413
9
1.84695
5
1.84447
7
1.45636
6

From the graph, k01 = 101.5328 = 34.51 dm3/mol/s and the slope of the graph = 1.7629.
Error Analysis:
Using LINEST to calculate the error in the slope:
Error in the intercept, 0.12934 for log k1 therefore log k1 / log k1 = k1 / k ,
Therefore k1 = 0.12934*74.5/1.872, = 5.14
Error in gradient = 0.876

Discussion:
The Kinetic Salt Effect affects the reaction through stabilization. For example in the above
reaction, both reactants have a charge. The negatively charged reactant is stabilized by the
positive charges from the salt, while the positively charged reactant is stabilized by the negative
charges from the salt. As a result the rate at which the reactants come together decreases, thus
decreasing the rate at which the carbinol forms. Since a charged intermediate will be stabilized in
the solution as well, the half life of the intermediate at equilibrium will increase causing the
reaction towards product formation. Since the rate of the product formation becomes higher
because of increased amounts of the intermediate present on the solution first order kinetics is
used to derive the rate constant equation:

Where,
is the charge on the cation and ion from the salt.

is a product value.

is the ionic strength. is also dependent on the solubility of the salt in the reaction mixture.
Ionic strength is directly proportional to the solubility of the salt. Changing the ionic strength
manipulates the solvation of the reactants and intermediates, thus changing the
, and
affecting the reaction rate. In this experiment, the lower the concentration of KNO3, the kinetic
salt, the lower the rate of the reaction and in the flask where there was no kinetic salt present, the
rate of the reaction slowed dramatically, as the there was no stabilizing effect for the Na+ and
OH- ions in solution. The value reached for the slope (1.7629) is higher but is relatively accurate
as the literature value (1.018) is taken at 298 K and this experiment was conducted at 302K.