STUDENTS NAME: RAFA KUSY THE DATE: 22.03.

2012

THE TITLE OF AN EXPERIMENT: RATE OF ISOMERIZATION REACTION

TRANS CIS OF [CR(C2O4)2(H2O)2]
-

1. THE PURPOSE OF AN EXPERIMENT

This experiment was aimed at order determination of isomerization reaction trans cis of [Cr(C2O4)2(H2O)2]- ion, finding its rate coefficient and a half time.

2. USED REAGENTS
Ammonia water solution Ethanol Oxalic acid dihydrate Perchloric acid Potassium dichromate(VI)

3. USED LABORATORY APPLIANCES

Analytical scale Beakers Crystallizer Cuvettes Flasks Funnels Glass rod Sintered glass filter Spectrometer Suction flask Volumetric flask Watch glasses Weighing bottles

4. CHEMICAL EQUATIONS
1) SYNTHESIS OF POTASSIUM CIS-[DIAQUABIS(OXOLATO)CHROMATE(III)] DIHYDRATE 7 ( H2C2O4 2H2O ) + K2Cr2O7 2 K Cr ( C 2O4 )2 ( H2O )2 2H2O + 6CO2 + 13H2O 2Cr VI + 6e 2CeIII 6C 6C + 6e
III IV

reduction oxidation

2) SYNTHESIS OF POTASSIUM TRANS-[DIAQUABIS(OXOLATO)CHROMATE(III)] TRIHYDRATE 7H2C2O4 + K 2Cr2O7 2 K Cr ( C2O4 )2 ( H2O )2 + 6CO2 + 3H2O
2Cr VI + 6e 2CeIII 6C 6C + 6e
III IV

reduction oxidation

K trans-Cr ( C2O4 )2 ( H2O )2 + 3H2O K Cr ( C2O4 )2 ( H2O )2 3H2O

5. MOLECULAR FORMULAS OF SYNTHESISED PRODUCTS

trans-K[Cr(C2O4)2(H2O)2]

cis-K[Cr(C2O4)2(H2O)2]

6. SUMMARY OF THE PROCEDURE

1) SYNTHESIS OF POTASSIUM TRANS-[DIAQUABIS(OXOLATO)CHROMATE(III)] TRIHYDRATE 1 g of potassium dichromate(VI) was solved in c.a. 2 cm3 of hot water. 3 g of oxalic acid dihydrate were solved in c.a. 6 cm3 of boiling water. Obtained solution was poured into previously prepared solution of potassium dichromate(VI). The beaker was covered with watch glass and left for a while. Obtained solution was left for a week to concentrate it. Obtained crystals were filtrated and rinsed respectively with small volume of cold water and ethanol. The product was dried and weighted. Purity of it was checked by putting small amount of crystals on filter paper strip and moistening them with the use of ammonia water solution.

2) SYNTHESIS OF POTASSIUM TRANS-[DIAQUABIS(OXOLATO)CHROMATE(III)] TRIHYDRATE 1 g of potassium dichromate(VI) and 3 g of oxalic acid dihydrate were grinded to powder by means of mortar. Obtained mixture was transferred into a crystallizer containing drop of water and it was covered with watch glass. After spontaneous reaction, small volume of ethanol was poured into obtained green, thick oil and the mixture was triturated with glass rod until crystals were formed. Product was filtrated and rinsed with small volume of ethanol. The product was dried and weighted. Purity of it was checked by putting small amount of crystals on filter paper strip and moistening them with the use of ammonia water solution.

3) MEASUREMENT OF ELECTRON SPECTRA 0.2 g of given isomer were solved in water so that volume of solution was equal 50 cm3. Spectra of those solutions were recorded in a range 350 - 700 nm using a cuvette filled with distilled water as a reference material. Both spectral position of absorption band maxima and absorbance were read off.

4) MEASUREMENT OF ISOMERIZATION RATE OF TRANS COMPLEX INTO CIS COMPLEX 0.2 g of trans isomer were solved in 10-4 M perchloric acid so that volume of solution was equal 50 cm3. Spectra of this solution were recorded in a range 350 - 700 nm every few minutes using a cuvette filled with 10-4 M perchloric acid as a reference material. Meanwhile, one tube filled to an half of its volume with the prepared solution was heated on water bath for 30 min. Spectrum of cooled solution from tube was recorded in the same way as previous spectra.

7. RESULTS
Results of the experiment were listed in below tables:
Table No.1 MEASUREMENT OF ELECTRON SPECTRA Isomer Wavelength [nm] 415 565 415 560 Absorbance A 0,838 0,602 0,579 0,458

cis trans

Table No.2 MEASUREMENT OF ISOMERIZATION RATE

OF TRANS COMPLEX INTO CIS COMPLEX

No. 1 2 3 4 5 6 7 8 9 10

Time t [s] 978 1174 1458 1637 1806 1977 2151 2315 2483

Wavelength [nm] 415 555 415 560 415 560 415 560 415 560 415 560 415 560 415 560 415 560 415 565

Absorbance A 0,423 0,348 0,465 0,377 0,509 0,408 0,530 0,423 0,551 0,439 0,567 0,450 0,582 0,460 0,597 0,469 0,606 0,478 0,707 0,571

8. THE ANALYSIS OF RESULTS

Molar absorption coefficients corresponding to the maxima which occurred at 415, 565 and 560 nm on absorption spectra were counted with the use of Beer-Lambert law:

A = c l
A absorbance mol c molar concentration 3 dm

[1]

molar absorbtion coefficient cm mol

dm3

l distance the light travels through the material [ cm]

In this case equation used to count molar absorption coefficients has shape as follows:

A c l

Molar concentration was counted using below relationship:

c=

n m = V M V

mol c molar concentration 3 dm n amount of constituent [ mol ] V volume of solution dm3 g M molar mass of constituent m m mass of constituent [ m ]
Results were gathered in below table:

Table No.3 COUNTED MOLAR ABSORPTION COEFFICIENTS Mass of specimen m [g] 0,1996 0,05 trans 357,21 0,2013 0,01127 Volume of Molar Distance Wavelength Absorbance solution concentration l [cm] [nm] A V [dm3] c [moldm-3] 0,01177 0,999 415 465 415 460 0,838 0,602 0,579 0,458 Molar absorbance coefficient [dm3cm-1mol-1] 71,3 51,2 51,4 40,7

Molar mass Isomer M [gmol-1]

cis

339,19

Values of absorbance (referring to wavelength equal 415 nm) and corresponding to them times were listed in below table. Table No.4 RESULTS OF KINETIC MEASUREMENT OF ISOMERIZATION REACTION Time t [s] 978 1174 1458 1637 1806 1977 2151 2315 2483

No. 1 2 3 4 5 6 7 8 9

A 0,423 0,465 0,509 0,530 0,551 0,567 0,582 0,597 0,606

A - A 0,2840 0,2420 0,1980 0,1770 0,1560 0,1400 0,1250 0,1100 0,1010

ln(A - A) -1,2588 -1,4188 -1,6195 -1,7316 -1,8579 -1,9661 -2,0794 -2,2073 -2,2926

(A - A)-1 3,5211 4,1322 5,0505 5,6497 6,4103 7,1429 8,0000 9,0909 9,9010

0,7070

To determine order of the isomerization reaction, integral rate equations were derived by integration of differential equations of given order: Zeroth-order reaction

co

dc =k dt
0

differential equation

dc = -k dt
c t

usage of definite int egrals

co initial concentration c-concentration in particular time

co c = kt

int egral equation

First-order reaction

co

dc = k c dt
0

differential equation

dc c = -k dt c t
c = kt co

usage of definite int egrals

co initial concentration c-concentration in particular time

ln

integral equation

[2]

Second-order reaction

co

dc = k c2 dt
0

differential equation

dc c2 = -k dt c t

usage of definite int egrals

co initial concentration c-concentration in particular time

1 1 = kt c co

integral equation

Subsequently, on base of data gathered in fourth table, charts corresponding to different kinetic equations were plotted:

0,30

A - A

0,25

0,20

0,15

A - A = -0,0001189t + 0,3814 R = 0,9691

0,10

0,05 t [s] 0,00 900 1100 1300 1500 1700 1900 2100 2300 2500

Chart No.1 DEPENDENCE OF (A - A) ON TIME

-1,1 ln(A - A) -1,3 -1,5 -1,7 -1,9 ln(A - A) = -0,0006865t - 0,6069 -2,1 -2,3 t [s] -2,5 900 1100 1300 1500 1700 1900 2100 2300 2500 R = 0,9988

Chart No.2 DEPENDENCE OF LN(A - A) ON TIME

10 9 8 7 6 5 4 3

(A - A)

-1

(A - A)-1 = 0,004241t - 0,9853 R = 0,984

t [s] 2 900 1100 1300 1500 1700 1900

-1

2100

2300

2500

Chart No.3 DEPENDENCE OF (A - A) ON TIME

As mentioned above plotted charts correspond to different kinetic equations. First chart refers to zeroth-order reaction, second one is connected with first-order reaction and the last one corresponds to second-rate reaction. Judging from obtained values of correlation coefficient squares, the most linear relationship presents chart no. 2 so dependence of ln(A - A) on time. In this case one may state that the isomerization reaction is a first-order reaction. Owing to directly proportionality of absorbance to molar concentration [1], molar concentration from rate equations was replaced with absorbance. Rate coefficient of the isomerization reaction was found as a negative slope of plotted line at second chart:

ln ( A A ) = a t + b ln ( A A ) = 0.0006865 t 0.6069
1 k = a = 0.0006865 s

linear equation linear equation from 2nd chart

rate coefficeinet

Expression which enables to count a half time of the isomerization reaction was found by substitution concentration in particular time - c for initial concentration - co divided by two [2]:

co ln 2 = k 1 2 co
In this case, a half time of the reaction equals:

=
1 2

ln 2 ln 2 = [ s ] = 1010 [ s ] k 0.0006865

9. YIELD OF THE REACTIONS

Mass of reagents used in the experiment:

mH2C2O4 2H2O = 1.00 g mK2Cr2O7 = 3.00 g

1) SYNTHESIS OF POTASSIUM CIS-[DIAQUABIS(OXOLATO)CHROMATE(III)] DIHYDRATE Determination which reagent was used in excess: 126.07 g 3.00 g H2C2O4 2H2O 294.19 g H2C2O4 2H2O mg K2Cr2O7 K2Cr2O7

m = 7.00 g

Above calculation shows that oxalic acid dihydrate was used in excess. Theoretical amount of potassium cis-[diaquabis(oxolato)chromate(III)] dihydrate that should have been obtained:

294.19 g 1.00 g

K 2Cr2O7 678.38 g K2Cr2O7 mtheo. g

K Cr ( C2O4 )2 ( H2O )2 2H2O K Cr (C 2O4 )2 ( H2O )2 2H2O mtheo. = 2.31 g

Quantity of obtained compound: mobt . = 1.74 g The yield of the reaction:

y= mobt . 1.74 g 100% = 100% = 75.3% mtheo. 2.31 g

2) SYNTHESIS OF POTASSIUM TRANS-[DIAQUABIS(OXOLATO)CHROMATE(III)] TRIHYDRATE Determination which reagent was used in excess:
90.04 g 3.00 g H2C 2O4 294.19 g H2C 2O4 mg K2Cr2O7 K2Cr2O7 m = 9.80 g K 2Cr2O7

Above calculation shows that oxalic acid was used in excess. Theoretical amount of potassium cis-[diaquabis(oxolato)chromate(III)] dihydrate that should have been obtained:

294.19 g 1.00 g

K 2Cr2O7 714.42 g K2Cr2O7 mtheo. g

K Cr ( C2O4 )2 ( H2O )2 3H2O K Cr ( C2O4 )2 ( H2O )2 3H2O mtheo. = 2.43 g

Quantity of obtained compound: mobt . = 1.65 g The yield of the reaction:

y= mobt . 1.65 g 100% = 100% = 67.9% mtheo. 2.43 g

9. PURITY OF PRODUCTS
Purity of both isomers was checked by test described in the procedure. Filter paper strips were attached below:

8. CONCLUSION
The exercise allowed prove the isomerization reaction trans cis of [Cr(C2O4)2(H2O)2]- ion is a first order reaction and to find its rate coefficient and a half time . During experiment, a directly proportional dependence of absorbance on molar concentration was used to measure changes of cis isomer molar concentration. Purity of synthesized products was satisfactory judging from the made test and attached strips. Moreover, absorption spectrum did not showed characteristic band corresponding to chromium. Concerning yields of reactions, they are not very satisfactory. This fact might have been caused by loses of products during filtration and purification processes. During performance of the experiment there was a possibility of commitment mistakes connected with: inaccurate preparation of solutions inaccurate measurement of absorbance insufficient purification of products

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