A Colorimetric Investigation of the Rate of Isomerization of trans-Potassium Dioxalatodiaquochromate(III) to the cis Isomer.

Levi Stanley and Andrew Aspaas 6 December, 2000

Advanced Inorganic Chemistry Dr. M. Lindbeck

Introduction: Through the use of UV-visible spectra, is it possible to determine the rate of isomerization of trans-potassium dioxalatodiaquochromate(III) to the cis isomer. Using the absorption data, a plot of absorption is used to determine the rate constant k for isomerization.

Theory: The absorbance A ofa solution of two absorbing species, at time t, is given by the following equation: At = l{X[X]t + Y[Y]t} The following equation gives the rate law, if X and Y are reactant and product, respectively: d[X] = k[X ] dt and, by integration [X]t = [X]0 e-kt where [X]t is the concentration of X at time t, and [X]0 is the initial concentration of X. Thus, the concentration of Y after time t is given by the following equation: (3) (2) (1)

[ Y]t = [ X ]0 [ X ]0 e kt
Substituting for [X]t and [Y]t in equation 1 gives: At = l { X [X]0 e -kt + Y[ X]0 Y[ X]0 e-kt } therefore At = { X Y }e - kt + E Y l[ X]0

(4)

(5)

(6)

therefore At (7) = Y = { X Y }e- kt l[ X]0 By plotting the left hand side of this equation against time, a straight line develops with slope k. This plot requires a knowledge of Y and [ X]0 . Since Y is unknown in this work, a different approach is needed. Let AT = absorbance of trans isomer and AC = absorbance of cis isomer. Then, A1 , A2 , A3 = absorbances of the isomerizaing solution at time t1 , t2 , t3 Similarly, Ai1 , Ai2 , Ai3 = the absorbances of the solution at times t1 + t, t2 + t, t3 + t From this follows: Ac A1 = ( Ac AT )e kt1 (8)

because ( Ac AT ) is a measure of initial concentration of the solution containing the trans isomer, and ( Ac A1 ) is a measure of the trans isomer remaining after time t1 . Thus,

(A (A
and
i 1

A1i ) = ( Ac AT )e

k ( t1 + t)

(9)

If equation 9 is subtracted from equation 8, the following result: A1 ) = ( Ac AT ) e kt 1 e

k ( t1 + t)

(10)

(A
and

i 1

A1 ) = ( Ac AT ) e kt 1 (1 e k t )

(11)

( Ac AT )
resulting in e
kt1

(A

i 1

A1 )

ekt 1 = 1 e kt

(12)

(1 e )( A A ) = (A A )
k t i 1 c T 1

(13)

By taking the natural log of both sides, the result is: kt1 = ln (1 e k t )( Ac AT ) ln( A1i A1 ) This can be reduced to kt = constant ln A where A is the difference in absorbance between the solutions at time t. By plotting ln A against time in seconds, a straight line should result, which should show the reaction is 1st order. The slope of this line is the rate constant, k. (14)

Experimental A solution of 10-4 M perchloric acid was prepared by adding 0.005 mL of concentrated perchloric acid to 50 mL nanopure water. 0.09 g of the trans isomer was dissolved into the perchloric acid solution. The UV-visible spectrum of this solution was recorded, initially at two-minute intervals, then at five-minute intervals. Finally, a spectrum was taken after two hours after complete isomerization had occurred.

Results and Discussion

Time 0 2 4 6 8 10 15 20 25 30 120 Time 0 120 240 360 480 600 900 1200 1500 1800 7200 Peak 1 int 0.16 0.166 0.183 0.196 0.206 0.219 0.236 0.247 0.259 0.269 0.35 Difference 0 0.006 -5.1159958 0.023 -3.7722611 0.036 -3.3242363 0.046 -3.0791139 0.059 -2.8302178 0.076 -2.5770219 0.087 -2.4418472 0.099 -2.3126354 0.109 -2.2164074 0.19 -1.6607312 ln A Peak 2 int 0.124 0.129 0.137 0.146 0.153 0.161 0.171 0.18 0.188 0.196 0.25 Difference 0 0.005 0.013 0.022 0.029 0.037 0.047 0.056 0.064 0.072 0.126 -5.2983174 -4.3428059 -3.8167128 -3.5404594 -3.2968374 -3.0576077 -2.8824036 -2.7488722 -2.6310892 -2.0714734 ln A

ln A vs t
0 0 -1 y = 0.001275x - 4.094812 -2 ln A -3 -4 y = 0.001260x - 4.520718 -5 -6 time (sec) 500 1000 1500 2000

The rate constant k was determined to be 0.0012675 at 25C. This is the average of the values obtained from the two peaks on the spectrum. The values of k were in good agreement, although the plots of ln A did not appear to be linear. This could be due to a number of factors, possibly including error in time measurement, isomerization over time during storage of the complexes, and temperature effects on isomerization in solution. There also was a possibility that the trans isomer was not 100% pure. Although the isomerization should theorectically be 1st order, the resultant graphs appear to deviate from this expected result. The isomerization may actually be second order due to effects that were not able to be accounted for. Further work could be done on this experiment with a thermostatted cell holder for the UV-Vis. This would allow rate constants at different temperatures to be

determined and data for calculation of activation energy and frequency factor for the reaction could be ascertained.

Reference: G. Pass, H Sutcliffe (1974), Practical Inorganic Chemistry. Chapman and Hall: London, 182-85.