Date Exercise number and Points

23.03.2023 title
30.03.2023 Ex. 18
Isomerization rate of Exam Execution Report
trans-cis transition of
[Cr(ox)2(H2O)2]- ion
Teaching Student
assistant Hubert Dziełak
Dr Grzegorz
Stopa

Isomerisation rate of trans-cis

transition of [Cr(ox)2(H2O)2]- ion
1 THE OBJECTIVE OF THE EXPERIMENT
The aim of exercise was to synthesize and characterise by measurement of UV-vis spectra and
kinetic of isomerisation two isomers of diaquadioxolatochromate(III) anion.

2 THEORETICAL INTRODUCTION

2.1 CHROMIUM OXIDATION STATES

The most common oxidation states for chromium are +2, +3, and +6. Their electron
configurations are presented in Figure 1.

Figure 1: Simplified d orbital splitting diagrams for chromium in different oxidation states and their most common geometries
(octahedral for +2 and +3, tetrahedral for +6)

Due to high stabilization of (t2g)3 configuration chromium(III) complexes are inert O(transition
states do not have octahedral geometry), which means that their synthesis have to be carried out
through other oxidation state chromium intermediate. In this particular exercise, that
intermediate was potassium dichromate.
2.2 ISOMERISM OF OCTAHEDRAL COMPLEXES
Octahedral geometry allows for many stereo and structural isomers. In this experiment, the
focus was put on the cis-trans structural isomerism. Such isomers can differ in physical and
chemical properties such as stability and absorbance in case of complex of interest of this
exercise. Isomers of [Cr(ox)2(H2O)2]- ion are shown in Figure 2.

Figure 2: cis-trans isomerism of [Cr(ox)2(H2O)2]-

2.3 KINETICS AND RATE DETERMINATION

The rate of reaction is the speed at which substrates are converted to products, it is a rate of
change that can be described by a differential equation. Rate is always proportional to some
constant 𝑘 and depending on its order can be also dependant on concentration of the substrates
and products. Elementary reactions can only be of the zeroth, first or second order (an extremely
unlikely case of the third order was observed1). General rate Equation (1):
𝑑𝑐
𝑣=− = 𝑘[𝐴]𝑎 [𝐵]𝑏 … (1)
𝑑𝑡
[𝐴], [𝐵], … − 𝑐𝑜𝑛𝑐𝑒𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑜𝑓 𝑟𝑒𝑎𝑔𝑒𝑡𝑠 [𝑀]
𝑎, 𝑏, … − 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑟𝑎𝑡𝑒𝑠, 𝑖𝑛 𝑐𝑎𝑠𝑒 𝑜𝑓 𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑎𝑟𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡𝑠.
Integrating equation (1) we can determine concentration dependence on time for common
orders (2), (3) and (4):
0°: 𝑐 = 𝑐𝑜 − 𝑘𝑡 (2)

1°: 𝑐 = 𝑐𝑜 𝑒 −𝑘𝑡 (3)

1 1
2°: = + 𝑘𝑡 (4)
𝑐 𝑐𝑜
Plotting concentration for 0° , natural logarithm of concentration for 1° and inverse of
concentration for 2° vs. time gives linear relationship. This way, it is possible to easily
determine order based on experimental data. In case of this experiment, the concentration was
not determined directly. Absorbance, which is linearly dependent on concentration and
described with Equation (5) known as Lambert-Beer law, was used instead:

1
Kerr, James Alistair. "Notes on the Tables." CRC Handbook of bimolecular and termolecular gas
reactions . Boca Raton, Florida: CRC Press, 1987. 2. Print
 𝐴 = 𝜀𝑙𝑐 (5)
1
𝜀 − 𝑎𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑎𝑛𝑡 𝑑𝑒𝑝𝑒𝑛𝑑𝑎𝑛𝑡 𝑜𝑛 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔ℎ𝑡 𝑎𝑛𝑑 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 [ ]
𝑀 ∙ 𝑐𝑚
𝑙 − 𝑝𝑎𝑡ℎ 𝑙𝑒𝑛𝑔𝑡ℎ [cm].

3 EXPERIMENT EXECUTION AND DATA

3.1 SYNTHESIS OF TRANS-K[CR(OX)2(H2O)2]·3H2O

In a 100 cm3 beaker 2.01 g of potassium dichromate in approximately 4 ml of boiling distilled
water (solution dried and water was replaced, fast rate of evaporation made determining the
exact amount of water impossible). In a separate 100 cm3 beaker, 6.01 g of oxalic acid dihydrate
was dissolved in 12 ml of hot distilled water. When both solutions were clear, oxalic acid with
plastic pipette was slowly added, stirring with a glass rod, to the beaker with dichromate
standing on a hot plate. When solutions mixed, vigorous reaction evolving gas were occurring
and solution darkened. When the whole solution was added, the beaker in which the reaction
took place was covered with watch glass. After approximately 5 minutes the solution was taken
off the hot plate and handed over to the preparatory room, where it was concentrated and cooled
down. Dark purple crystals formed. The crystals were filtered on a G3 fritted glass filter, washed
with a small amount of ethanol and approximately 4 ml of ice cold water. 3.88 g of product
were obtained. A test for presence of other isomer was conducted: small amount of powdered
product was placed on filter paper and few drops of diluted ammonia solution were added. The
product did not dissolve but the paper edges became grey, which may indicate slight
contamination with the cis isomer. The paper used for the tests is depicted in Figure 3.

Figure 3: Test of isomeric purity for the trans isomer of [Cr(ox)2(H2O)2]-

3.2 SYNTHESIS OF CIS-K[CR(OX)2(H2O)2]·2H2O

Oxalic acid dihydrate and potassium dichromate were crushed to a fine powder as possible
using mortar and pestle. In the crystalizing dish, 3.67 g of powdered oxalic acid was mixed with
1.00 g of potassium dichromate. Reaction vessel was placed on the hot plate with watch glass
as a cover. After a short period of time, heated mixture started violently reacting. A black paste
has formed. A small amount of ethanol was added and the product was mixed with glass rod.
When most of the substance hardened contaminated alcohol was replaced, mixed again and
final portion of ethanol was added. The product was poured into watch glass covered with four
layers of filter paper and left to dry in open air. 1.06 g of grey powder were obtained and the
same purity test was performed as for the trans complex. The compound dissolves giving a grey
solution and there are few orange stains that are visible, most likely due to contamination with
potassium dichromate. The result is presented in Figure 4.

Figure 4: Test of isomeric purity for the cis isomer of [Cr(ox)2(H2O)2]-

3.3 UV-VIS SPECTRA AND MEASUREMENT OF THE ISOMERISATION KINETICS

Spectra were measured for solutions prepared by following procedures:

3.3.1 cis-[Cr(ox)2(H2O)2]-
To 50.0 cm3 volumetric flash 0.2004 g of cis-K[Cr(ox)2(H2O)2]·2H2O were added and the
weighing dish was thoroughly rinsed with water, which was poured into the flask. The flask with
about one third of the final volume of water added was closed with a well-fitting cap and vigorously
shaken until the complex salt dissolved. The volumetric flask was filled to the calibration line and
mixed several times by turning it upside down.

3.3.2 trans-[Cr(ox)2(H2O)2]- in water

To 50.0 cm3 volumetric flash 0.2006 g of trans-K[Cr(ox)2(H2O)2]·3H2O were added and the
weighing dish was thoroughly rinsed with water, which was poured into the flask. The flask
with about one third of the final volume of water added was closed with a well-fitting cap and
vigorously shaken until the complex salt dissolved. The volumetric flask was filled to the
calibration line and mixed several times by turning it upside down. It is important to use this
solution as soon as possible because of slow isomerisation to cis form.
Both solutions are depicted in Figure 5.

Figure 5: Solutions of similar concentrations of cis (right) and trans (left) [Cr(ox)2(H2O)2]-
3.3.3 trans-[Cr(ox)2(H2O)2]- in diluted HClO4
To 50.0 cm3 volumetric flash 0.2004 g of trans-K[Cr(ox)2(H2O)2]·3H2O were added and the
weighing plate was thoroughly rinsed with 10-4 M HClO4 in water, which was poured into a
flask. The flask with about one third of the final volume of acid added was closed with a well-
fitting cap and vigorously shaken until the complex salt dissolved. The volumetric flask was
filled to the calibration line and mixed several times by turning it upside down. It is important
to use this solution as soon as possible because of isomerisation to cis form.

3.3.4 cis-[Cr(ox)2(H2O)2]- in diluted HClO4

A test tube was filled to about one forth with previously prepared trans-[Cr(ox)2(H2O)2]- in
diluted HClO4. The solution was placed in a beaker with hot water and placed on a hot plate.
For the first 5 minutes, there was too much of the solution and heating was insufficient. After
adjusting the conditions, the solution was heated for 31 minutes.
The solutions prepared this way were measured in UV-vis spectrometer. Cuvettes with a path
length of 1.00 cm were rinsed a few times with solutions being measured to ensure that only
the desired solution was measured. The results of the measurements of complexes in water are
presented in Table 1.
Table 1: UV-vis spectra results for aqueous solutions of cis and trans [Cr(ox)2(H2O)2]-

Peak 1 Absorbance 1 Peak 2 Absorbance 2

cis-[Cr(ox)2(H2O)2]- 565.5 nm* 0.606 415 nm 0.846
-
trans-[Cr(ox)2(H2O)2] 556 nm 0.328 414 nm 0.411
*Average value in plateau of the peak
To determine kinetics of the reaction the same solution of acidified trans complex were
measured every approximately two minutes. In addition, acidic solutions were measured with
comparison: a solution of 10-4 M solution of perchloric acid. Due to the effect of temperature
on reaction speed, the heated solution is treated as one that was measured for 𝑡 → ∞. Only peak
near 415 nm were measured. The results are shown in Table 2.
Table 2: Absorbance and time of measurement since preparation of solution of trans-[Cr(ox)2(H2O)2]- in 10-4 M HClO4

No. Time [min: s] Absorbance

1 5:49 0.246
2 7:10 0.268
3 8:01 0.277
4 10:08 0.301
5 11:34 0.313
6 13:28 0.321
7 14:38 0.330
8 16:05 0.343
9 16:58 0.351
10 18:57 0.368
11 20:50 0.383
12 22:47 0.397
13 24:56 0.411
14 26:49 0.426
15 28:39 0.439
16 30:36 0.452
 17 32:33 0.474
18 34:50 0.483
19 37:53 0.494
20 40:15 0.505
21 41:55 0.512
22 43:20 0.519
23 45:25 0.530
∞ 0.768

4 DATA ANALYSIS

4.1 SYNTHESIS CHEMISTRY AND YIELD

4.1.1 trans-K[Cr(ox)2(H2O)2]·3H2O
Synthesis can be divided into two main steps: reduction-oxidation step and crystallisation:
The first step is described by the following reaction:
2− −
7 𝐻2 𝐶2 𝑂4(𝑎𝑞) + 𝐶𝑟2 𝑂7(𝑎𝑞) ⟶ 2 [𝐶𝑟(𝐶
⏟ 2 𝑂4 )2 (𝐻2 𝑂)2 ](𝑎𝑞) + 3 𝐻2 𝑂(𝑙) + 6 𝐶𝑂2(𝑔)
𝑡𝑟𝑎𝑛𝑠
− +
𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛: 𝐻2 𝐶2 𝑂4(𝑎𝑞) ⟶ 2 𝐶𝑂2(𝑔) + 2 𝑒 + 2 𝐻(𝑎𝑞)
2− + −
𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛: 𝐶𝑟2 𝑂7(𝑎𝑞) + 4 𝐻2 𝐶2 𝑂4(𝑎𝑞) + 6 𝑒 − + 6 𝐻(𝑎𝑞) ⟶ 2 [𝐶𝑟(𝐶
⏟ 2 𝑂4 )2 (𝐻2 𝑂)2 ](𝑎𝑞) + 3 𝐻2 𝑂(𝑙)
𝑡𝑟𝑎𝑛𝑠

Crystallization from concentrated solution proceeds in following manner:

− +
[𝐶𝑟(𝐶
⏟ 2 𝑂4 )2 (𝐻2 𝑂)2 ](𝑎𝑞) + 𝐾(𝑎𝑞) + 3 𝐻2 𝑂(𝑙) → 𝐾[𝐶𝑟(𝐶
⏟ 2 𝑂4 )2 (𝐻2 𝑂)2 ] ∙ 3 𝐻2 𝑂(𝑠)
𝑡𝑟𝑎𝑛𝑠 𝑡𝑟𝑎𝑛𝑠
1
The yield was calculated based on the amount of oxalic acid used ( 𝑛𝑜𝑥 =
7
g
6.81 𝑚𝑚𝑜𝑙 𝑣𝑠. 𝑛𝐾2𝐶𝑟2 𝑂7 = 6.83 𝑚𝑚𝑜𝑙 ). Molar mass was calculated 𝑀𝑡𝑟𝑎𝑛𝑠 = 357.201 mol
and yield was determined using equation (6):
𝑚𝑡𝑟𝑎𝑛𝑠 3.88
𝑀𝑡𝑟𝑎𝑛𝑠 357.201
𝜂𝑡𝑟𝑎𝑛𝑠 = ∙ 100% = ∙ 100% = 79.8% (6)
2 2 ∙ 6.810 ∙ 10−3
∙ 𝑛
7 𝑜𝑥
4.1.2 cis-K[Cr(ox)2(H2O)2]·2H2O
In solid state synthesis of cis complex only one main step can be assigned. The chemical
reaction describing it is shown:
7 𝐻2 𝐶2 𝑂4 ∙ 2 𝐻2 𝑂(𝑠) + 𝐾2 𝐶𝑟2 𝑂7(𝑠) ⟶ 2 𝐾[𝐶𝑟(𝐶
⏟ 2 𝑂4 )2 (𝐻2 𝑂)2 ] ∙ 2 𝐻2 𝑂(𝑠) + 17 𝐻2 𝑂(𝑙 𝑜𝑟 𝑔) + 6 𝐶𝑂2(𝑔)
𝑐𝑖𝑠
1
The yield was calculated based on the amount of potassium dichromate used (7 𝑛𝑜𝑥 =
g
4.16 𝑚𝑚𝑜𝑙 𝑣𝑠. 𝑛𝐾2 𝐶𝑟2𝑂7 = 3.40 𝑚𝑚𝑜𝑙). Molar mass was calculated 𝑀𝑐𝑖𝑠 = 339.185 and
mol
yield was determined using equation (7):
 𝑚𝑐𝑖𝑠 1.06
𝑀𝑐𝑖𝑠 339.185
𝜂𝑐𝑖𝑠 = ∙ 100% = ∙ 100% = 46.0% (7)
2 ∙ 𝑛𝐾2 𝐶𝑟2𝑂7 2 ∙ 3.399 ∙ 10−3

4.1.3 Concentrations of the solutions used in UV-vis measurements

Concentration of solutions used were calculated using molar masses from sections 4.1.1 and
4.1.2. The values are shown in Table 3.
Table 3: Concentrations of solutions used for UV-vis measurements

trans- trans-
cis-[Cr(ox)2(H2O)2]-
[Cr(ox)2(H2O)2]- in [Cr(ox)2(H2O)2]- in
in water
water diluted HClO4
𝑐 [10−3 M] 1.18 1.12 1.12

4.2 UV-VIS SPECTROSCOPIC DATA ANALYSIS

4.2.1 Aqueous solution spectroscopic data
The molar absorption coefficients were calculated using equation (8) derived from the
Lamber-Beer law (5) and the concentrations calculated in Section 4.1.3.
𝐴
𝜀= (8)
𝑙𝑐
The values with wavelengths of the corresponding peaks are presented in Table 4.
Table 4: Molar absorption coefficients for peaks in UV-vis spectra of cis and trans [Cr(ox)2(H2O)2]-

Peak 1 [nm] 𝜀1 [M −1 cm−1 ] Peak 2 [nm] 𝜀2 [M −1 cm−1 ]

-
cis-[Cr(ox)2(H2O)2] 565.5 514 415 717
trans-[Cr(ox)2(H2O)2]- 556 293 414 367
4.2.2 Kinetics Determination Using UV-vis data
To determine the order of the rate equation describing isomerisation, three plots were drawn.
The values calculated from the raw data from Table 2 used to prepare these graphs are
presented in Table 5. The time of the first measurement was set as 0 and the absorbance of the
heated sample has been used as 𝐴∞ .
Table 5: Data used to plot the time dependency of absorbance

1
𝑡 [s] 𝐴∞ − 𝐴 ln(𝐴∞ − 𝐴)
𝐴∞ − 𝐴
0 0.522 -0.650 1.92
71 0.500 -0.693 2.00
122 0.491 -0.711 2.04
249 0.467 -0.761 2.14
335 0.455 -0.787 2.20
449 0.447 -0.805 2.24
519 0.438 -0.826 2.28
606 0.425 -0.856 2.35
659 0.417 -0.875 2.40
778 0.400 -0.916 2.50
891 0.385 -0.955 2.60
 1008 0.371 -0.992 2.70
1137 0.357 -1.030 2.80
1250 0.342 -1.073 2.92
1360 0.329 -1.112 3.04
1477 0.316 -1.152 3.16
1594 0.294 -1.224 3.40
1731 0.285 -1.255 3.51
1914 0.274 -1.295 3.65
2056 0.263 -1.336 3.80
2156 0.256 -1.363 3.91
2241 0.249 -1.390 4.02
2366 0.238 -1.435 4.20

Data from Table 5 are plotted and depicted in Figure 6.

4.5
A∞ - A ln(A∞- A) 1/(A∞- A)
−0.6
0.5 Linear fit Linear fit Linear fit
4.0

−0.8
3.5

1/(A∞- A)
ln(A∞- A)

0.4
A∞- A

−1.0 3.0

2.5
0.3 −1.2
y = (0.498) + (-0.000117) * x y = (-0.665) + (-0.000328) * x y = (1.83) + (0.000950) * x
A∞- A ln(A∞- A) 1/(A∞- A)
Pearson's r -0.993235 Pearson's r -0.998845 Pearson's r 0.994748
2.0
Adj. R-Square 0.985874 Adj. R-Square 0.99758 Adj. R-Square 0.989024
Intercept 0.498 ± 0.004 −1.4 Intercept -0.665 ± 0.005 Intercept 1.83 ± 0.028
Slope -1.17E-4 ± 3E-6 Slope -3.28E-4 ± 3E-6 Slope 9.50E-4 ± 2.1E-5
0.2 1.5
0 1000 2000 3000 0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500
Time (s) Time (s) Time (s)

Figure 6: Linear fits for the 0th (left, blue), 1st (centre, red) and 2nd (right, green) order.

From values of adjusted R2 – parameter of goodness of fit, it can be determined that the first
order best fits experimental data. In Figure 7 a full-sized graph is shown.
 ln(A∞- A)
−0.6
Linear fit

ln(A∞- A) −0.8

−1.0

−1.2
y = (-0.665) + (-0.000328) * x
ln(A∞- A)
Pearson's r -0.998845
Adj. R-Square 0.99758
−1.4 Intercept -0.665 ± 0.005
Slope -3.28E-4 ± 3E-6

0 500 1000 1500 2000 2500

Time (s)

Figure 7: Linear dependence of ln(A∞ - A) and time

Slope of linear fit in case of first order reaction is equal to −𝑘. From this relationship rate
1
constant is determined 𝑘 = 3.28 ∙ 10−4 s . Using equation (9) half-life of trans complex was
calculated.
ln 2
𝑡1 = = 2110 s = 35.2 min (9)
2 𝑘

5 SUMMARY
Syntheses of trans and cis diaquadioxolatochromate(III) potassium salts were carried out. The
reaction yields were decent, but the cis complex was likely contaminated with the starting
material. UV-vis spectra were measured and based on change in absorbance rate constant were
calculated. Reaction was determined to be first-order.