Kinetics by Colorimetry

Experiment #3
Chemistry 1552/M,T,TH
June 2, 2015

By: Christian Triand

Lab Partner: Keila Hamed-Ramos

Lab Instructor: Richard Jarman

Concept of Experiment:
Students will use a colorimeter to determine different rates of reaction of
Crystal Violet (CV) with NaOH/NaCl solutions at different temperatures. By doing
this, students should see how the rate of reaction varies with different
temperatures. This is because, as a chemists rule of thumb, increasing the
temperature will likely increase the rate of reaction in a solution. By the end of the
experiment, students should have enough data to find the order in respect to OH and CV+. Students will also be able to calculate, through their graphs and data, k obs
and activation energy (Ea).

Brief Experimental Method:

Fill out two 250 ml beaker half full with distilled water. Place a thermometer in
both. Place one beaker on a hot plate. Obtain 12 test tubes and fill 4 with 1 mL of
0.1 M NaCl and 1mL of 0.1 M NaOH. Fill another 2 with 2 mL of .2 M NaOH. Finally,
fill 6 with 2mL 3.0 x 10^-5 M (CV). Place 4 CV in the room temperature bath, and 2
in the hot bath. Place 2 of the NaOH/NaCl in the room temp solution, the other two
in the hot bath, and the final 2 test tubes of NaOH in the room temperature bath.
Make sure the hot bath is only about 10-20 degrees higher than the room
temperature bath.
Set up a colorimeter to its Green LED function and use 2 cuvettes filled with
water to adjust the colorimeter. Students will mix the room temperature NaOH/NaCl
with CV twice, the hot bath NaOH/NaCl with CV twice, and the NaOH and CV at room
temperature twice. Record the temperature before mixing every time and then
record the data via the colorimeter to a usb drive for collection.

Results:
The charts were made given our gathered data. Kobs was determined using the
slope of the line (after testing for order wrt CV). Note that all concentrations below
are in M and rate is in MoleL^-1xSec^-1, sec^-1, or L Mole^-1/sec^-1 depending on
zeroth, first, or second order respetively.

Testing for Zeroth Order In Experiment One

0.4
0.35
0.3
0.25
Absorbance 0.2
0.15
0.1
0.05
0

100

200

300

400

Time (s)

Testing For First Order In Experiment One

0
-0.5

0 50 100 150 200 250 300 350

-1

Absorbane -1.5
-2
-2.5
-3

Time (s)

Experiment One (first order)

0
-0.5

-1

Absorbance -1.5

50 100 150 200 250 300 350

f(x) = - 0.01x - 0.91

-2
-2.5
-3

Time

Testing For Second Order In Experiment One

15
10

Absorbane

5
0

50 100 150 200 250 300 350

Time (s)

Experiment Three (First Order)

0
-0.5

50

100 150 200 250

-1

Absorbance -1.5

f(x) = - 0.01x - 1.02

-2
-2.5
-3

Time (s)

Experiment Two (1st Order)

0
-0.5
-1

Absorbance -1.5

50 100 150 200 250 300

f(x) = - 0.01x - 0.86

-2
-2.5
-3

Time (s)

Experiment Five (First Order)

0
-0.5
-1

Absorbance -1.5

20 40 60 80 100 120 140 160

f(x) = - 0.01x - 0.89

-2
-2.5
-3

Time (s)

Experiment Four (First Order)

0
-0.5

50

100 150 200 250

-1

Absorance -1.5

f(x) = - 0.01x - 1.02

-2
-2.5
-3

Time (s)

Experiment Six (First Order)

0
-0.5

50

100

150

-1

Absorbance -1.5 f(x) = - 0.01x - 0.98

-2
-2.5
-3

Time (s)

K
Concentrat Concentrat Observ Calculated K
ion CV
ion OH
ed
values
0.0000125
0.05 0.0058
0.116
0.0000125
0.05
0.006
0.12
0.0000125
0.05 0.0092
0.184
0.0000125
0.05 0.0073
0.146
0.0000125
0.1 0.0112
0.112
0.0000125
0.1 0.0144
0.144

The graphs above show that wrt CV it is in the first order. Using the slope to
find Kobs, the K values can also be calculated (see table above). The order of
OH can also be calculated using the table above. Through dividing the
concentrations of CV and OH as well as the KObs of the averages in trial 1+2
with the averages in trial 5+6, we find that the rate roughly doubles (2.169)
when OH is doubled. After calculations, the order comes out to 1.12, which
can be seen as first order wrt OH. The temperatures for solving for activation
energy are annexed at the end of this lab report. Finally, using the average

Kobs for trials 1+2 and 3+4, activation energy was calculated using equation
#3 with a product 16.287 KJ/mol /mol.

Equations:

1.Rate = (-d[CV+]/dt) = k[CV+]x[OH-]y

2.
K = Ae-Ea/RT
3. Ea = -R ((ln(k2/k1))((1/T2)-(1/T1)))
4. A = bC
5. Rate = k[CV+]x[OH-]y = kobs[CV+]x
where
- y
kobs[OH ]
6.
Zeroth order: [CV+]x = - kobs t +[CV+]o
7. First order: ln[CV+]x = - kobs t +ln[CV+]o
8. Second order: (1/[CV+]x ) = - kobs t +(1/[CV+]o)
9. Zeroth order: A = -kobsebt + Ao
10.
First order: lnA = -kobst + lnAo
11.
Second order: (1/A) = (-kobs/b) + (1/Ao)
12.
(kobs(trial2)/kobs(trial1)) = (k[OH- (Trial2)]y/k[OH(trial1)]y)
Calculations:
For calculating order wrt OH, see the information used below. Averages were used
from trials 1+2 as well as 5+6. The equation used to determine the Conc CV, Conc
OH, and rate was Equation #12. This the end result of this is 2^m = 2.169. Taking
the natural log of each side and dividing ln2.169 with ln2 gives the number 1.12.
This represents first order wrt OH. Sample calculations are seen below.

ri
rf

factors after the rate

equation
Concentration Concentration
CV
OH
rate
2.1694
1
2
92

0.0059
0.0128
1.25ECvi
05
1.25ECvf
05
Ohi
0.05
Ohf
0.1
Sample calculation for finding K:

K
Concentrat Concentrat Observ Calculated K
ion CV
ion OH
ed
values
0.0000125
0.05 0.0058
0.116

K can be found by taking K observed / Concentration OH. So .0058 / .05 = .116

For Ea, using equation #3:

ln (k2 / k1) = (Ea / R) ( (1/T1) - (1/T2) )

For my trial 2, my average k obs was .00825. For my trial 1, my average k
obs was .0059. My average temperature for T1 was 20.5*C, while my
average temperature for T2 was 36.6*C. Once converted into Kelvin for the
equation, I got 293.65 and 309.15 K respectively. I'm using 8.134 for R. I took
these averages from trials 1+2, and 3+4 respectively.
ln (.00825/.0059) = (Ea / 8.134) ( (1/293.65) - (1/309.15) )
.335 = (Ea / 8.314) (.000171)
2.79 = Ea x .000171
Ea = 16287 j/mol = 16.287 KJ/mol

The temperatures used were from data recorded during lab. Please see annexed
sheet.