Experiment 1: The Kinetics of

Methylene Blue Reduction by Ascorbic

Acid
Introduction
The reaction of methylene blue and ascorbic acid is very convenient to study for the purpose of
developing a rate equation because it reacts to form Leucomethylene blue and dehydroascorbic acid
and the solution becomes colourless. The progress of the reaction may be monitored by measuring
the absorbance of the 666nm band using a spectrophotometer. The rate law for this reaction is

Which by using excess ascorbic acid, can be simplified to:

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 1: Sample i + stock

Time (s) Absorbance [MB+]
ln[MB+] 1/[MB+]
0 0.00758408 1.02488E-07 -16.0935 9757282
7 0.00551752 7.45611E-08 -16.4116 13411815
14 0.00436532 5.89909E-08 -16.6459 16951777
21 0.00312097 4.21753E-08 -16.9814 23710560
28 0.00342026 4.62197E-08 -16.8899 21635788
35 0.00260043 3.5141E-08 -17.1639 28456824
42 0.00325926 4.4044E-08 -16.9381 22704557
49 0.00252375 3.41047E-08 -17.1938 29321500
56 0.00254325 3.43682E-08 -17.1861 29096656
63 0.00239335 3.23425E-08 -17.2469 30919050
70
0.0021548 2.9119E-08 -17.3519 34341869
77 0.00256179 3.46187E-08 -17.1789 28886087
84 0.00247824 3.34897E-08 -17.212 29859956
91 0.00228935 3.09371E-08 -17.2913 32323626
98 0.00218324 2.95032E-08 -17.3388 33894591
105
0.002363 3.19324E-08 -17.2596 31316154
112 0.00217549 2.93985E-08 -17.3423 34015385
119 0.00229833 3.10584E-08 -17.2874 32197360
Table 2: Sample i+v
Time (s) Absorbance [MB+]
ln[MB+] 1/[MB+]
0 -0.0018966 2.56291E-08 -17.4795 39018094
7 -0.0016786 2.26833E-08 -17.6016 44085320
14 -0.0016793 2.2693E-08 -17.6012 44066365
21 -0.0020277 2.74009E-08 -17.4127 36495088
28 -0.0016881 2.28122E-08 -17.596 43836159
35 -0.0019975 2.69929E-08 -17.4277 37046827
42 -0.0025033 3.3829E-08 -17.2019 29560415
49 -0.0021935 2.96421E-08 -17.3341 33735794
56
-0.002006 2.71085E-08 -17.4234 36888841
63 -0.0019702 2.66238E-08 -17.4415 37560440
70 -0.0021583 2.9166E-08 -17.3503 34286547
77 -0.0024396 3.29671E-08 -17.2278 30333259
84 -0.0017994 2.43159E-08 -17.5321 41125270
91 -0.0029615 4.00201E-08 -17.0339 24987461
98 -0.0021016 2.84001E-08 -17.3769 35211093
105 -0.0024173 3.26659E-08 -17.2369 30612996
112
-0.002205 2.97966E-08 -17.3289 33560831
119
-0.002102 2.84057E-08 -17.3767 35204190

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 4: Sample iii

Time (s) Absorbance [MB+]
ln[MB+] 1/[MB+]
0 0.13193744 1.78294E-06 -13.2372 560871.9
7 0.11778738 1.59172E-06 -13.3507 628250.6
14 0.10535432 1.42371E-06 -13.4622 702391.7
21 0.09320424 1.25952E-06 -13.5848 793955.3
28 0.08274017 1.11811E-06 -13.7039 894366.1
35 0.07339875 9.91875E-07 -13.8237 1008192
42
0.0646525 8.73682E-07 -13.9505 1144581
49 0.05621075 7.59605E-07 -14.0905 1316474
56 0.04907416 6.63164E-07 -14.2262 1507922
63 0.04329541 5.85073E-07 -14.3515 1709188
70 0.03820938 5.16343E-07 -14.4765 1936697
77 0.03316868 4.48225E-07 -14.618 2231021
84 0.02946336 3.98154E-07 -14.7364 2511594
91 0.02553615 3.45083E-07 -14.8795 2897853
98 0.02300473 3.10875E-07 -14.9839 3216729
105
0.0201221 2.7192E-07 -15.1178 3677549
112 0.01739969 2.35131E-07 -15.2631 4252949
119 0.01635662 2.21035E-07 -15.3249 4524163

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

Table 6: Sample iv (replicate)

Time (s) Absorbance [MB+]
ln[MB+] 1/[MB+]
0 0.28327635 3.82806E-06 -12.4732
261229
7 0.27230865 3.67985E-06 -12.5126 271750.5
14 0.26274538 3.55061E-06 -12.5484 281641.5
21 0.25246993 3.41176E-06 -12.5883 293104.2
28 0.24299042 3.28365E-06 -12.6266 304538.8
35
0.2328576 3.14672E-06 -12.6691 317790.8
42 0.22362465 3.02195E-06 -12.7096 330911.6
49 0.21368688 2.88766E-06 -12.7551 346301.1
56 0.20494427 2.76952E-06 -12.7968 361073.8
63 0.19590648 2.64738E-06 -12.8419 377731.3
70 0.18742625 2.53279E-06 -12.8862
394822
77 0.17821193 2.40827E-06 -12.9366
415236
84 0.17018387 2.29978E-06 -12.9827 434823.8
91 0.16231708 2.19347E-06
-13.03 455897.8
98 0.15459691 2.08915E-06 -13.0788 478664.2
105 0.14668903 1.98228E-06 -13.1313 504468.5
112 0.14006153 1.89272E-06 -13.1775 528339.2
119 0.13293631 1.79644E-06 -13.2297 556657.5

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 iii)

y = 0.0022x - 17.52
R = 0.3046

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

[Ascorbic Acid in curvette]

0.2830189M
0.1415094M
0.0566038M
0.0566038M
0.0283019M

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

[Ascorbic Acid] (mol/L)

Figure 5: Shows kobs with respect to the Ascorbic Acid Concentration

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

0.03M Ascorbic Acid

Stock Solution 1.3*10-4M Methylene Blue

)
(
(

Half life is 3828 seconds

)
)