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Computer-Interfaced Experiments - Absorbance Measurement

Kinetics
Reaction of Methyl Orange with Tin(II) Chloride - Pseudo First Order Reaction

Objective: Determination of Rate Constants and Activation Parameters

Peter Keusch



Datalogging and data analysis using the Program CHEMEX and the
Analog-Digital-Converter CHEMBOX IBK electronic + informatic
IBK electronic + informatic

German version





Chemicals:
0.001 M aqueous methyl orange
conc. HCl
SnCl2 · 2 H2O

0.2 M SnCl2 solution:  25 g of SnCl2 · 2 H2O are dissolved in 21.8 mL of conc. HCl. The solution is made up to 1 L with dist. water.

Apparatus and glass wares:
magnetic stirrer hotplate
3 magnetic stirring bars
stirring bar remover
crystallizing dish d = 190 mm, h = 90 mm  (for water bath)
contact thermometer
thermometer 0 - 50 °C  (resolution: 0.1 °C)
2 volumetric flasks 1000 mL
2 beakers 50 mL
2 volumetric pipettes 20 mL
2 pipette bulbs
micropipette
diode photometer  (IBK)
plastic cuvettes 10 mm × 10mm × 45 mm (Sarstedt)

Hazards and safety precautions:

Conc. HCl is extremely corrosive. Inhalation of vapour can cause serious injury. Ingestion may be fatal. Liquid can cause severe damage to skin and eyes.
Sn(II) chloride is harmful if swallowed. Eye, skin and respiratory irritant.

Safety goggles and gloves must be worn. The experiment should be performed in a well ventilated room. The SnCl2 solution should be prepared under a fume !


Theoretical background:

SnCl2 reduces methyl orange in strongly acidic solution to form p-amino benzene sulfonic acid and p-dimethyl-amino aniline


Fig. 1: Fading of methyl orange with Sn 2+


Hence the reaction can be monitored by measuring the methyl orange absorbance as a function of time. Under the given conditions (see procedure - large excess of one of the reactants) the reaction is pseudo first order.


Kinetic equations (Download PDF file)













Calibration of the photometer and the matching of the program Chemex are carried out, as described in experiment  Fading of Phenolphthalein in Alkaline Solution.

The wavelength is set to 470 nm.


Experimental procedure:

Experiment set-up
Fig. 2: Experiment set-up
20 mL of a 0.001 molar aqueous solution of methylorange are pipetted into a beaker. 20 mL of 0.2 M SnCl2 solution are transferred into a further beaker. The two beakers are placed in a water bath, in which a contact thermometer and a thermometer with a resolution of 0.1 °C are immersed  (Fig. 2).  A reaction temperature below the room temperature is obtained and maintained by careful addition of ice or cold water to the water bath. After thermal equilibrium has been reached (15 minutes) the reaction temperature is read.

2 mL of the thermostated SnCl2 solution is pipetted into a cuvette. 1 mL of the thermostated solution of methylorange is added. The cuvette covered with a slide plate is inverted 2-3 times to ensure a proper mixing. If necessary the outside of the cuvette is wiped to dry. Immediately the cuvette is placed into the sample compartment of the photometer (l = 470 nm) and the sensing software is started. The measuring interval is 1 second.

The absorbance maximum of methyl orange is 410 nm. The used diode photometer IBK provides light emitting diodes with the wavelengths 660 nm (red), 565 nm (green) and 470 nm (blue).

The change in transmittance is displayed simultaneously on the measuring screen.



The in-situ determination of the reaction rate on the basis of a continuous logging of photometrical data is allowed in rapid reactions (small change in temperature during te reaction).



evaluation screen
Fig. 3: Multigraph screen    overlay of the transmittance curves
1:  7 °C     2:  10 °C     3:  14 °C     4:  21 °C



Data analysis using Excel
(Download) - determination of the rate constants and the activation parameters:


An Excel function is used to convert the transmittances into absorbances and lnA values (Tab. 1). A plot of -lnA versus t is generated  (Fig. 4).


Excel
Tab. 1: Measured values T (t)    calculation of -lnA


proportional constant
Fig. 4: Determination of the proportional constant k'  
1:  7 °C     2:  10 °C     3:  14 °C)



Messung

T [ °C ]
k' [ s-1 ]
k [ L · mol -1 · s -1 ]
1
7
0.0455
0.3033
2
10
0.0548
0.3653
3
14
0.0676
0.4507
Tab. 2: Calculation of the rate constant k
(According to the reaction conditions: k = k' / 0.15)


If the reaction temperatures and the corresponding rate constants are entered into the table of the Excel file   Activation parameters (Download), then all activation parameters  (Tab. 3)   will be calculated and in a diagram the plot according to ARRHENIUS and EYRING will be constructed  (Fig. 5).


activation parameters
Tab. 3: Calculation of the activation parameters


Arrhenius and Eyring
Fig. 5: ARRHENIUS (1) and EYRING plot (2)



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