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The rate can then be determined using the integration rate method.
Aim:
To investigate the rate of reduction of methylene blue by ascorbic acid in an acid solution using a
spectrophotometer and to use kinetic data to determine the rate law and rate constant for the
reaction.
Experimental:
The experiment was conducted using the method outlined in the Laboratory Manual. There were no
deviations from this method.
Results
Tables 1-6 show the absorption of light with a 666nm wavelength with respect to time for ascorbic
acid solution reacted with methylene blue. The progression of the reaction to completion was shown
by the reduction of the absorption. The concentration was calculated by dividing the absorbance by
the molar absorption coefficient for methylene blue at 666nm (7*104cm-1M-1)
Table 3: Sample ii
Time (s) Absorbance [MB+]
ln[MB+] 1/[MB+]
0 0.14356169 1.94002E-06 -13.1528 515457.8
7 0.11384028 1.53838E-06 -13.3848 650033.5
14 0.08886733 1.20091E-06 -13.6324
832702
21 0.06795935 9.1837E-07 -13.9007 1088886
28 0.05194603 7.01973E-07 -14.1694 1424556
35 0.03812843 5.15249E-07 -14.4786 1940809
42 0.02831628 3.82652E-07 -14.7761 2613337
49 0.02068993 2.79594E-07 -15.0899 3576619
56 0.01470723 1.98746E-07 -15.4312 5031539
63 0.01078242 1.45708E-07 -15.7417 6863025
70 0.00807329 1.09098E-07 -16.031 9166029
77 0.00605953 8.18855E-08 -16.3179 12212170
84 0.00434642 5.87354E-08 -16.6502 17025506
91 0.00352169 4.75903E-08 -16.8606 21012667
98 0.00280076 3.78481E-08 -17.0897 26421386
105 0.00250877 3.39024E-08 -17.1998 29496472
112 0.00167715 2.26642E-08 -17.6025 44122460
119 0.00167562 2.26435E-08 -17.6034 44162832
Table 5: Sample iv
Time (s) Absorbance [MB+]
ln[MB+] 1/[MB+]
0
0.3096365 4.18428E-06 -12.3842 238989.9
7 0.29964125 4.04921E-06 -12.417
246962
14 0.28600043 3.86487E-06 -12.4636 258740.9
21 0.27620903 3.73255E-06 -12.4984
267913
28 0.26503235 3.58152E-06 -12.5397 279211.2
35 0.25443867 3.43836E-06 -12.5805 290836.3
42 0.24547322 3.31721E-06 -12.6164 301458.5
49
0.2353999 3.18108E-06 -12.6583 314358.7
56 0.22531193 3.04476E-06 -12.7021 328433.6
63 0.21591029 2.91771E-06 -12.7447 342734.9
70 0.20657706 2.79158E-06 -12.7889 358219.8
77 0.19689605 2.66076E-06 -12.8369 375832.8
84 0.18739258 2.53233E-06 -12.8864 394892.9
91 0.17932196 2.42327E-06 -12.9304 412665.6
98 0.17044851 2.30336E-06 -12.9811 434148.7
105 0.16192316 2.18815E-06 -13.0325 457006.9
112
0.1541322 2.08287E-06 -13.0818 480107.3
119 0.14636263 1.97787E-06 -13.1335 505593.5
Figure 1
1.200E-07
1.000E-07
[MB+] (mol/L)
8.000E-08
y = -4E-10x + 6E-08
R = 0.5572
6.000E-08
[MB+]
[MB+]
Linear ([MB+])
4.000E-08
2.000E-08
0.000E+00
0
20
40
60
80
100
120
140
Time (s)
Figure 1: Shows the concentration of methylene blue in solution i with respect to time
Figure 2
-16.00
0
20
40
60
80
100
120
140
-16.20
ln[MB+] (mol/L)
-16.40
-16.60
y = -0.0152x - 16.385
R = 0.8223
-16.80
Sample i
ln[MB+]
-17.00
Linear
(Sample i)
-17.20
-17.40
-17.60
Time (s)
Figure 2: Shows the natural log concentration of methylene blue in solution i with respect to time
Figure 3
4.000E+07
3.500E+07
3.000E+07
2.500E+07
2.000E+07
1/[MB+]
1.500E+07
1.000E+07
5.000E+06
0.000E+00
0
20
40
60
80
100
120
140
Figure 3: Shows the inverse of the concentration of methylene blue in solution i with respect to time
Figures 2 is the straightest of figures 1-3 for solution i, indicating that the order of reaction with
respect to methylene blue is a first-order reaction and this is supported by the linearity shown in the
sample (i+v) through to sample iv plot (figure 4). The non-linear sections will be ignored for
calculating the linear regressions in order to calculate the kobs.
Figure 4
0.00
0
20
40
60
80
100
120
140
-2.00
-4.00
Sample i+v
ln[MB+] (mol/L)
-6.00
Sample ii
-8.00
Sample iii
-10.00
Sample iv
y = -0.0064x - 12.453
R = 0.9978
-12.00
Sample iv
(replicate)
Linear (Sample
y = -0.0181x - 13.212 i+v)
R = 0.9994
Linear (Sample ii)
-14.00
-16.00
-18.00
-20.00
y = -0.0399x - 13.132
R = 0.9951
Linear (Sample iv
(replicate))
Time (s)
Figure 4: Shows the natural log concentration of methylene blue in solutions (i+v)-iv with respect to
time
Table 7
Solution
i
ii
iii
iv
iv (repl)
[Initial Solution]
0.30M
0.15M
0.06M
0.03M
0.03M
kobs
-1.52E-02
-3.99E-02
-0.0181
-0.0064
-0.0064
Average
k
-5.37E-02
-2.82E-02
-3.20E-01
-1.13E-01
-2.26E-01
-0.199
Figure 5
0.00E+00
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
-5.00E-03
-1.00E-02
K obs
-1.50E-02
-2.00E-02
Series1
-2.50E-02
-3.00E-02
-3.50E-02
-4.00E-02
-4.50E-02
Figure 7 shows that if the outlier for solution ii is ignored the kobs is proportional to the concentration
of ascorbic acid so its order is 1. Table 7 shows the rate constants calculated from the various
concentrations and their average. k=kobs/[ascorbic acid]1
Discussion/ Conclusion
The data obtained in this experiment was not satisfactory. The plots for solutions ii and i+v could not
be satisfactorily transformed into straight lines so it was difficult to fit decent linear regression lines.
As the rest of the analysis was dependant on the kobs derived from these plots, the rest of the results
are considered unreliable, however when these data points were ignored in figure 5, so a conclusion
could be reached.
Potential sources for the unreliable data could be:
-The methylene blue should have been added to the curvette when it was in the machine so there
was not a delay in starting the absorption plotting.
-Other variables that may not have been controlled carefully enough include the reactant
temperature and the solution concentration.
References
Appendix
Exercises:
1. The kobs changed significantly when the concentration of methylene blue changed (-1.52E-02
for 1.3*10-4 M methylene blue and -3.99E-02 for 6.5*10-5M methylene blue. This is what was
expected as a change in the initial concentration should change the rate of reaction. The kobs
is the slope of the concentration of methylene blue with respect to time i.e. the rate that
methylene blue disappears. So if the rate changes the rate methylene is used changes so
should the kobs
2)
3)
4)
Solution iv
)
(
(
)
)