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Topic: Qn on Pseudo-order rate equations  (Read 3051 times)

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Offline Landy813

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Qn on Pseudo-order rate equations
« on: January 06, 2009, 01:40:41 PM »
Hello all i need some help with this,

The oxidation of benzhydrol, (C6H5)2CHOH, in a basic solution of potassium permanganate, KMnO4, has the following time-independent stoichometry:

(C6H5)2CHOH(aq) + 2MnO4 (aq) + 2OH−(aq) = (C6H5)2CO(aq) + 2MnO4 2−(aq) + 2H2O  (reaction 1)

The reaction was followed by monitoring the decrease in benzhydrol concentration (we will refer to this as ‘BH’ for short) as a function of time. The results of an experiment carried out at 298.2 K are given in Table 1. The initial concentrations of reactants are as follows:

[BH]0 = 3.9 × 10−4 mol dm−3
[MnO4 ]0 = 7.8 × 10−4 mol dm−3
[OH]0 = 2.2 × 10−2 mol dm−3

For Reaction 1 the initial concentration of OH− was 2.2 × 10−2 mol dm−3and the partial orders with respect to BH and MnO4 are equal to 1. Thus, if the concentrations of BH and MnO4 are related as follows:

[BH]0 = [MnO4]0/2

show how the general rate equation you suggested in part (c) can be
simplified to give the following pseudo-order rate equation


Can anyone tell me what the number 2 means in this equation

J= 2KR'[BH]2

is it there are 2 reactants in excess if i use the the initial rate method.

Regards

Landy

Offline Hunt

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Re: Qn on Pseudo-order rate equations
« Reply #1 on: January 06, 2009, 03:04:43 PM »
The "2" is added because in this case [MnO4-] = 2[BH] at any time.


Because the concentration of hydroxide ions is much greater than the concentrations of other reactants , you can do an approximation and assume [OH]- is a constant. Then the rate J = k'[BH][MnO4-]

If [BH] = [BH]o - x then

[MnO4-] = [MnO4-] o - 2x

Initially 2 [BH]o = [MnO4-]o

[MnO4-] = 2 [BH]o - 2x = 2 [BH]

so J = 2k' [BH]2

Offline renge ishyo

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Re: Qn on Pseudo-order rate equations
« Reply #2 on: January 06, 2009, 03:07:51 PM »
I think it refers to a substitution made (the two comes from the stoichiometry of the balanced chemical equation).

If the initial equation can be written as (assuming first order for both BH and Mn04):

J = KR[BH]0[Mn04]0

using the equation based on the stoichiometry to solve for the concentration of Mn04:

[Mn04]0 = 2[BH]0

substitute in for [Mn04]0 in J:

J = KR[BH]0(2[BH]0) or upon rearrangement:

J = 2KR[BH]02

Edit: Blarg, too slow I guess  :-[

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