Why is the Arrhenius plot for the rate constant different from y=e-1/x?

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Discussion Overview

The discussion revolves around the differences between the Arrhenius plot of the rate constant (k) versus temperature (T) and the mathematical form of the equation y=e^{-1/x}. Participants express confusion regarding the shape of the Arrhenius plot and seek clarification on why it appears different from the expected graph based on the latter equation.

Discussion Character

  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • One participant expresses confusion about the Arrhenius plot, noting that it should resemble the graph of y=e^{-1/x} but finds it differs significantly.
  • Another participant suggests that the bottom chart of the Arrhenius plot, which plots 1/T versus ln(k), is the correct interpretation, while the upper chart shows T versus k.
  • Some participants propose that the activation energy (Ea) may change with temperature, potentially causing the upward curvature observed in the plot.
  • One participant shares a graph from WolframAlpha that resembles the expected shape but questions its validity over a broader temperature range.
  • Another participant explains the derivation of the linear relationship between ln(k) and 1/T, introducing constants c1 and c2, which leads to further questions about their definitions.
  • Clarifications are made regarding the nature of the straight line approximation used in the context of the Arrhenius equation.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the reasons behind the differences in the plots. Multiple competing views regarding the interpretation of the Arrhenius plot and the behavior of the rate constant remain unresolved.

Contextual Notes

Some participants express uncertainty about the relationship between activation energy and temperature, as well as the implications of the constants introduced in the linear approximation.

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Homework Statement


This isn't a homework question but this thing is disturbing from a long time.
I attended a class on Arrhenius equation and its plots. One of the plots is disturbing me from long which is the plot between k vs T.
Arrhenius equation:-
k=Ae^{-\frac{E_a}{RT}}
k->Rate constant
Ea->Activation Energy
R->Gas constant
T->Temperature

Homework Equations


The Attempt at a Solution


Since the equation is of the form y=e-1/x, the graph should be like this one:-
Click Here
But my teacher made a completely different plot. I constantly said that it shouldn't be like that. Finally, when i checked wikipedia, to my surprise, the teacher was right. Here's the wiki article:- http://en.wikipedia.org/wiki/Arrhenius_plot
I don't understand why the graph is different from that of y=e-1/x? Can somebody tell me where i am going wrong?

Thanks!
 
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I am talking about this graph from the wiki page:-
625px-NO2_Arrhenius_k_against_T.svg.png


No, i don't think this one is log based.
 
okay so the bottom chart is an arrhenius plot plotting 1/T vs ln(k) as defined in the wiki page and the upper chart is the same data but plotting T vs k.

The only thing I can think of is that Ea changes with the square of T causing it to curve upward.
 
Hey Pranav-Arora! ;)

Here's another one from WolframAlpha.


http://www4c.wolframalpha.com/Calculate/MSP/MSP82681a10gc2589cc12cc00000dh1e4827i034cf8?MSPStoreType=image/gif&s=20&w=300&h=183&cdf=RangeControl

plot[ y=e^(-1/x), {x,0.2,0.5} ]


Doesn't it kind of look like your graph?
 
Last edited by a moderator:
I like Serena said:
Hey Pranav-Arora! ;)

Here's another one from WolframAlpha.


http://www4c.wolframalpha.com/Calculate/MSP/MSP82681a10gc2589cc12cc00000dh1e4827i034cf8?MSPStoreType=image/gif&s=20&w=300&h=183&cdf=RangeControl

plot[ y=e^(-1/x), {x,0.2,0.5} ]

Doesn't it kind of look like your graph?

Hello ILS! :)

Oh yeah, that's look like something which i am looking for. You made the graph for very small values of x but i don't think that this is correct because in the wiki graph, temperature is increasing to high numbers but it isn't turning like to be that of y=e^(-1/x).

jedishrfu said:
okay so the bottom chart is an arrhenius plot plotting 1/T vs ln(k) as defined in the wiki page and the upper chart is the same data but plotting T vs k.

The only thing I can think of is that Ea changes with the square of T causing it to curve upward.

Ea changes with the square of T? I will have to check that out.
 
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Well, the formula is undoubtedly based on the shape of the graph when plotting ln k versus 1/T.
Then you apparently get the graph:

500px-NO2_Arrhenius_lnk_against_T%5E-1.svg.png


This is approximated by a straight line.

With the relationship ##\ln k = c_1 - c_2 \cdot \frac 1 T##, you can deduce that ##k=A e^{-\frac B T}##.

When I make an approximation of this, I get the following graph:

http://www3.wolframalpha.com/Calculate/MSP/MSP65161a10geiaaagg40a900000h0fa40fba06a13c?MSPStoreType=image/gif&s=30&w=300&h=191&cdf=RangeControl
plot[ k=18e9 * e^(-13000/t), {t,590,660} ]Doesn't this kind of fit the expected graph?
 
Last edited by a moderator:
I like Serena said:
With the relationship ##\ln k = c_1 - c_2 \cdot \frac 1 T##...

How did you get this relation? :rolleyes:
 
Pranav-Arora said:
How did you get this relation? :rolleyes:

A straight line is defined by the equation:
$$y = a x + b \qquad\qquad (1)$$
where ##a## is the slope of the line, and ##b## is the y-coordinate where the line intersects the y-axis (the y-intercept).When we fit a straight line to a set of points, we try to find out what ##a## and ##b## have to be.In this case we have ##\ln k## on the y-axis, and ##\frac 1 T## on the x-axis.
So we replace ##y## in equation (1) by ##\ln k##, and we replace ##x## by ##\frac 1 T##.

The result is:
$$\ln k = a \cdot \frac 1 T + b$$

Since we already know that the line slopes down, I have taken the liberty of putting in a minus sign, and rewriting the equation with different constants ##c_1## and ##c_2## as:
$$\ln k = c_1 - c_2 \cdot \frac 1 T$$
 
  • #10
I like Serena said:
A straight line is defined by the equation:
$$y = a x + b \qquad\qquad (1)$$
where ##a## is the slope of the line, and ##b## is the y-coordinate where the line intersects the y-axis (the y-intercept).


When we fit a straight line to a set of points, we try to find out what ##a## and ##b## have to be.


In this case we have ##\ln k## on the y-axis, and ##\frac 1 T## on the x-axis.
So we replace ##y## in equation (1) by ##\ln k##, and we replace ##x## by ##\frac 1 T##.

The result is:
$$\ln k = a \cdot \frac 1 T + b$$

Since we already know that the line slopes down, I have taken the liberty of putting in a minus sign, and rewriting the equation with different constants ##c_1## and ##c_2## as:
$$\ln k = c_1 - c_2 \cdot \frac 1 T$$

I already knew about the straight line stuff, i was getting confused with those constant c1 and c2.
Thank you for the help! :smile:
 

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