Exp 1 - Reaction Kinetics of Bromination of Acetone

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The key takeaways are to determine the rate, order and activation energy of the bromination of acetone reaction.

The objective of the experiment is to determine the rate, order and activation energy of the bromination of acetone.

The rate law determined for the bromination of acetone is Rate = k[acetone][H+][Br2]-5

LABORATORY REPORT

SKF 3033: PHYSICAL CHEMISTRY II


Semester 2 Session 2017/2018

1. ABDUL RAHIM BIN MD SAAD


ID NUMBER & NAME (D20162075593)
2. MUHAMAD AZIB BIN MD ALLADZHAR
(D20162076205)

LECTURER DR NORLAILI BINTI ABU BAKAR

EXPERIMENT NO. 1

TITLE REACTION KINETICS OF BROMINATION OF ACETONE

DATE & DAY

CHECK LIST (Please tick) Marks


Title 5
Objective(s) 5
Methods 10
Results (Observation, Data, 30
Calculation, etc.)
Discussions and questions & 35
answers (if appropriate)
Conclusion(s) 10
References (at least 2) 5
TOTAL MARKS 100

Department of Chemistry
Faculty of Science and Mathematics
UNIVERSITI PENDIDIKAN SULTAN IDRIS
Title : Reaction Kinetics of Bromination of Acetone
Objectives : To determine the rate, order and activation energy of the bromination of
acetone
Methods : Refer jotter
Results :
Part A (at room temperature)
NO OF TRIAL TIME FOR REACTION TO COMPLETE
1 5 mins
2 7 mins 20 secs
3 6 mins 50 secs

Part B (at room temperature)


NO OF EXPERIMENT NO OF TRIAL TIME FOR REACTION TO
COMPLETE
1 1 300 secs
2 440 secs
3 410 secs
2 1 570 secs
2 584 secs
3 585 secs
3 1 216 secs
2 192 secs
3 214 secs
4 1 156 secs
2 136 secs
3 136 secs

Part C
TEMPERATURE NO OF TRIAL TIME FOR REACTION TO
COMPLETE
40°C 1 48 secs
2 51 secs
3 50 secs
45°C 1 28 secs
2 26 secs
3 27 secs
50°C 1 20 secs
2 19 secs
3 19 secs

Data Processing & Calculation:


𝐴𝑐𝑒𝑡𝑜𝑛𝑒 + 𝐵𝑟2 + 𝐻 + → 𝐴𝑐𝑒𝑡𝑜𝑛𝑒 − 𝐵𝑟 + 𝐻 + + 𝐵𝑟 −
𝑑[𝐴𝑐𝑒𝑡𝑜𝑛𝑒 − 𝐵𝑟] 𝑑[𝐵𝑟2 ]
𝑟𝑎𝑡𝑒 = =−
𝑑𝑡 𝑑𝑡
0.004𝑀
𝑟𝑎𝑡𝑒 =
440𝑠 + 410𝑠
( )
2
𝑟𝑎𝑡𝑒 = 9.41 × 10−6 𝑀. 𝑠 −1

No. of Exp Rate [acetone] [Br2] [H+]


Exp 1 9.41 × 10-6 0.8 0.004 0.2
Exp 2 1.03 × 10-6 0.8 0.006 0.2
Exp 3 1.93 × 10-5 0.8 0.004 0.4
Exp 4 2.80 × 10-5 1.2 0.004 0.4

From equation of reaction,


Rate law = k[acetone]x[Br2]y[H+]z

𝐸𝑥𝑝 2 1.03 × 10−6 𝑘[0.8]𝑥 [0.006] 𝑦 [0.2]𝑧


= =
𝐸𝑥𝑝 1 9.41 × 10−6 𝑘[0.8]𝑥 [0.004] 𝑦 [0.2]𝑧
0.109 = 1.5𝑦
𝑦 = −5
𝐸𝑥𝑝 4 2.80 × 10−5 𝑘[1.2]𝑥 [0.004] 𝑦 [0.4]𝑧
= =
𝐸𝑥𝑝 3 1.98 × 10−5 𝑘[0.8]𝑥 [0.004] 𝑦 [0.4]𝑧
1.45 = 1.5𝑥
𝑥=1
𝐸𝑥𝑝 3 1.93 × 10−5 𝑘[0.8]𝑥 [0.004] 𝑦 [0.4]𝑧
= =
𝐸𝑥𝑝 1 9.41 × 10−6 𝑘[0.8]𝑥 [0.004] 𝑦 [0.2]𝑧
2 = 2𝑧
𝑧=1
Therefore,
𝑅𝑎𝑡𝑒 = 𝑘[𝑎𝑐𝑒𝑡𝑜𝑛𝑒][𝐻 + ][𝐵𝑟2 ]−5

Temperature (K) 1/T (10-3. K-1) Rate ln Rate


296 3.38 9.41 × 10-6 -11.57
313 3.19 8.00 × 10-5 -9.43
318 3.14 1.48 × 10-5 -8.82
323 3.10 2.07 × 10-5 -8.48

Since both rate and rate constant expressing the change of concentration with time. When the
initial concentration is the same for each temperature, rate ≈ rate constant.

From graph,
𝐸𝑎
𝑚=
𝑅
𝐸𝑎
9833.3𝐾 −1 =
𝑅
𝐽
𝐸𝑎 = 9833.3𝐾 −1 × 8.314
𝐾. 𝑚𝑜𝑙
𝐽
𝐸𝑎 = 81751.56
𝑚𝑜𝑙
Discussion:
The bromination of acetone in acid solution proceeds according to
𝐴𝑐𝑒𝑡𝑜𝑛𝑒 + 𝐵𝑟2 + 𝐻 + → 𝐴𝑐𝑒𝑡𝑜𝑛𝑒 − 𝐵𝑟 + 𝐻 + + 𝐵𝑟 −
The reaction is catalysed by hydrogen ion. The rate is determined by
𝑑[𝐴𝑐𝑒𝑡𝑜𝑛𝑒−𝐵𝑟] 𝑑[𝐵𝑟2 ]
𝑟𝑎𝑡𝑒 = =− because Br2 is the limiting reactant.
𝑑𝑡 𝑑𝑡

The rate for this particular reaction at 23°C is 9.41 × 10-6 M.s-1.
The rate law is assumed to be of the form
Rate law = k[acetone]x[Br2]y[H+]z
where k is the rate constant and [A] represents concentration of A in moles liter-1. The
exponents x, y, and z indicate the order of the reaction with respect to acetone, bromine, and
hydrogen ion, respectively.
From the result and calculation, we know the order of each reactant which is 1 for Acetone, -
5 for Bromine and 1 for hydrogen ion. When a partial order is negative, the overall order is
usually considered as undefined. In this experiment, although the rate equation found is
𝑅𝑎𝑡𝑒 = 𝑘[𝑎𝑐𝑒𝑡𝑜𝑛𝑒][𝐻 + ][𝐵𝑟2 ]−5, the rate equation is more complex than that of a simple
order reaction.
Rate of the reaction is also determined at several temperatures in this experiment. By plotting
ln rate vs 1/T, the activation energy is calculated from the graph which is
𝐽 𝐽
81751.56 which is in good agreement with reported literature values (86700 𝑚𝑜𝑙)
𝑚𝑜𝑙

The biggest problem encountered during this experiment involves the difficulties in keeping
reactant concentrations constant when preparing the solutions and keeping temperature
constant when performing each of the reactions.

Conclusion:
In this experiment we able to determine the rate of bromination of acetone at 23°C which is
9.41 × 10-6 M.s-1. The order cannot be determined due to the complex nature of the partial
𝐽
order of its reactant and the activation energy is determined as 81751.56 .
𝑚𝑜𝑙
References:

Atkins, P., & de Paula, J. (2006). Physical Chemistry, Eighth Edition. New York: Oxford
University Pres

Catch, J. R., Elliott, D. F., Hey, D. H., & Jones, E. R. H. (1948). 66. Halogenated ketones.
Part I. The bromination of acetone and methyl ethyl ketone. Journal of the Chemical Society
(Resumed), 272-275.

King, K. D., Golden, D. M., & Benson, S. W. (1970). Kinetics of the gas-phase thermal
bromination of acetone. Heat of formation and stabilization energy of the acetonyl radical.
Journal of the American Chemical Society, 92(19), 5541-5546.

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