How can separation factor (RL), calculated through Langmuir isotherm model, serve as an invaluable factor in the adsorption process?

Dear Mojtaba,

I have also seen the parameter in several good articles but in my opinion, this is not conclusive. I have not so far seen any system where RL>1 is reported.

I appreciate your comment/question.

Hi Mojtaba,

I will analyze each case in separate, according to the R_L definition you showed [ R_L=1/(1+C₀*k) ]:

I hope this is clear!

Dear Yogesh,

Thank you for your support. In fact, I struggled with this question in my previous works, and even I used this factor in my first ISI paper to show that the adsorption process is favorable.

I am really optimistic that we can reach a concrete solution to this question.

Hi Fernando,

I am really grateful that you participate in my discussions.

As I said in the explanation, the value of 0<=R_L<=1 is acceptable, and you described each part separately, and I really appreciate it. But for the R_L>1 I couldn't get it.

Do You mean that we could have a negative value for K_L? (we definitely know with a negative value for constant rate, the denominator would be less than 1).

In every typical adsorption process, we have a contaminated solution, and we will use fresh adsorbent to remove those contaminations (In laboratory scale). So after the equilibrium time, finally we could only accept R_L=1 as an asymptote, which is a sign of no adsorption! let me explain it in another way: There is no adsorbate molecule on the adsorbent that could be released during the process (This is the only condition that we could accept desorption). Can you recommend any papers that had R_L>1 with a fresh adsorbent?

Therefore, what I am inclined to mention here is that in adsorption process with the fresh adsorbent, we should not even mention R_L>1. However, if the adsorbent is previously used and contains some adsorbate molecules attached to its particles, we can accept the desorption hypothesis and K_L lower than zero.

I hope I could convey the main confusing part of this equation.

Hi Mojtaba,

Thanks for following the discussion.

As I said, the only way in that R_L>0 is by desorption. Desorption cannot occur if there is nothing already adsorbed (as you correctly state). So, you are right saying that with fresh adsorbent R_L>0 cannot occur.

Note: I edited my comment above, to fix the correct condition as -1 < C₀*k < 0 instead of simply C₀*k < 0.

Dear Fernando,

Now it is much clearer, and both of us agreed on this statement that in adsorption with a fresh adsorbent, R_L>1 is not possible.

Thank you for this helpful discussion.

Very nice and interesting discussion. Thanks for your sharing, Fernando and Mojtaba. 

Thanks dear Ziadi

I appreciate your kind comment, I hope this will help you

nice discussion

so far no one has pointed if Rl<0 then what would be the condition

Dear Susmita,

I am of the opinion that the opportunity to discuss this challenging parameter is missing. I personally expect it from researchers to consider this discussion in their future works.

Best regards.

Dear All,,

i have found a Langmuir equation like this y = 8.454x - 4.365 and R² = 0.815 where the value of k is -4.37. Is it correct?

Dear Nur, Did you try different isotherm models such Freundlich, Elovich, etc? Because the coefficient of determination (R²) calculated here is not high enough to suppose that Langmuir is able to correlate the experimental data.

Dear Mojtaba,

I read the discussion between you and Mr. Fernando and I enjoyed it very much.

Your examples are about public adsorption, but in the case of specialized absorbents such as MIPs (molecularly imprinted polymers), this phenomenon may happen. You can refer to this paragraph from the reference below:

" It is well known that template residues are present in the polymer matrix even after exhaustive washing steps and leakage of the template can affect the accuracy of detection in trace analysis.To overcome this bleeding problem the MIP can be synthesized by using a close structural analogue of the analyte as template (also called dummy template) that can capture also the target analyte since very similar cavities are generated"

from:

in acidic condition template residues in the polymer matrix, may will have desorption in equilibrium solution, as a result KL<0 and RL>1.

Best wishes.

Dear all brothers, read all the discussion which is very fruitful but i have the same problem can any one tell me how to find out the value of k, can any one give me a brief detail i will be very thankful to you.

Dear Saleem,

We all are happy you found this discussion useful.

I see you have a question about finding K value in Langmuir isotherm. If so, when one obtained isotherm experimental data, he can do the regression to find out which model works better. The one in which the higher (R2) value is found fits the experimental data more accurate. This is how researcher can go for hypothesis and theory behind that model and conclude some results etc.

You can find thousand papers in this area. Should you need more help please don't hesitate to add your comment here.

Could anyone help me regarding the issues:

1). In one adsorption experiment, I got the ∆G (kJ/mol) values as below.

-8521.47 (288K)

-9073.61(298K)

-9624.52(308K)

This actually indicate that the reaction is spontaneous and favorable.

My inquire is what is standard value of ∆G (kJ/mol)?

2). Another inquire, what is the standard value of

∆H (kJ/mol) and ∆S (kJ/mol) in thermodynamics? There is any limit??

Thank you in advance for your opinion.

How does one deal with a situation where the correlation coefficient (R2) is as high as 0.99 yet the Langmuir Isotherm constant K gives negative value? Do we say the model failed to described the data despite the high R2 value or are there other reasons? Please, I will appreciated prompt contributions from all.

I think that there is a factor which might cause RL to be higher than 1, and it is the agitation speed. In an adsorption system, if you increase agitation speed using the same adsorbent already adsorbed with any amount of adsorbate, there is the possibility that higher speed rates may lead the ion or molecule to unbind from the surface and return to the solution, mainly if it is a physisorption process which is weaker and reversible. It will make the constant to be negative at some point of the process. The effect may be minimal, but I think it is possible. I don't know if there is already, but research regarding this topic would be interesting.

Dear Danilo,

Thank you for your contribution.

According to RL formula, and given the fact that we do not analyse the concentration during the process in isotherm experiments, I believe 0<RL<1.

However I disagreed with your reason, it it does not mean it is incorrect. I would be more than happy to understand the concept you are referring to.

Regards,

Mojtaba

Dear Shahjalal,

You can find the definition of standard value in the text books.

I know there is a range of ∆H for physisorption and chemisorption, indicating the nature of adsorption based on its value. You may find the same for other parameters in the literature.

Sorry couldn't be of help.

Dear Olanrewaju,

I am grateful for your comment.

I personally have never faced a negative value for K in my works. You are recommended to check other models as well.

Please share your new findings in this area to all of us.

Thank you.

Dear Fernando,

Thanks so much for your nice and useful answer.

Thank you Mojtaba Hedayati Marzbali for raising this query! Keerthanan Santhirasekaram apt for you!

A dimensionless constant called the equilibrium parameter can be used to express the important characteristics of the isotherm as follows:

where KL is the Langmuir constant and C0 is the initial solute concentration . The value of RL shows if the adsorption process is favorable or not as follows:

Dear Mojtaba Hedayati Marzbali,

thank you very much for this question since I was struggeling with the separation factor, too.

I want to add an enlighting information I found in the book of Eckhard Worch (2012).

In short, RL > 1 is possible because the factor is not necessarily derived from the Langmuir equation but it can always be used in it.

"In this way, any isotherm can be formally reduced to a Langmuir isotherm with a constant separation factor, R*. Such an isotherm transformation can be advantageous because for the case R* = constant, several analytical solutions for breakthrough curve models exist. It has to be noted that the formal application of Equation [...] to other isotherms can lead to separation factors of R* > 1, a range that is originally not covered by the Langmuir isotherm. For the Langmuir isotherm, R* is always lower than 1 [...]."

R* = RL

Dear Daniel Dittmann

Thank you for providing us with this valuable information. We are getting some new information now. Much appreciated.

Regards.

useful information

Dear All,

I am so grateful for your contributions concerning the subject matter particularly the issue of -be RL values. I am currently working on P adsorption in biochar amended soils and I have observed -ve RL values which have been worrisome. But I now understand the cause; most biochars has the tendency of adding P to the soil. Hence, I experienced P-desorption in those soils with exceptions of controls without biochar amendments.

Dear Augustus Ilori ,

Thank you for your support, and also sharing your finding with us.

my contribution is late, hopefully not too late.

Separation factor is about separation (of 2 components).

https://goldbook.iupac.org/terms/view/S05614 gives reasonable definition for chromatography, but it is also defined for liquid-liquid distribution https://goldbook.iupac.org/terms/view/S05615

also used for adsorption (mixture of binary adsorbates)

No idea who first got the idea to 'misuse' it for a one component adsorbate to try to double information already included in adsorption constant.

This is then combined with poor mathematics here in current discussion

' RL= 0 : This occurs if k is very very large' - no it gets small but never 0 , but it might be even be compensated by very small initial concentration, very large k does not mean irreversibility

k=0 is not linear adsorption it is no adsorption

negative k is not really defined - Langmuir adsorption isotherm is not for desorption.

If I do not miss a point RL provides no additional benefit.

The value of RL can calculate by the following eq.:

RL=1/(1+C0*k)

Its value should be 0<RL<1.

The value of RL shows if the adsorption process is favorable or not accordining the following values:

makes no sense to repeat answers of others, even more when R_L > 1 'unfavorable adsorption' - is impossible

Ihsan Habib Dakhil

We use different Co (initial conc.) for Langmuir isotherm modeling data i.e. Co=100, Co=300, Co=500 and Co=800. Then which Co would be use for RL ??

Moubarek Mebarki Ihsan Habib Dakhil Have you figure this yet? I also used different initial concentration (Co) for the isotherm study. Which concentration do we pick? Or is it not possible to calculate RL with different Co?

Moubarek Mebarki Ungku Amirul Arif Ungku Abdullah

You can draw RL versus different initial concentration ( Co ) at optimum conditions of other parameters which selected in your study.

Hi, I have a similar problem when I am applying Langmuir Isotherm on different concentrations of dye, and is obtaining RL =2.001 for all the adsorbates showing Langmuir adsorption is unfavourable and R2 value is equal to 0.9975 and 1.00 in some cases. I am using Rl=1/1+(1+ Kl*C0) formula.

Kindly guide in this regard

Irum, read the answers carefully and you should see it is all nonsense.

Here is link

It is very interesting discussion regarding the separation factor for the adsorption process and very good topic of research to avoid the confusion on separation factor. But I am still confused why these parameters are used to support the adsorption process.

I agree with Fernando Vallejos-Burgos

@Dr. Asif, in you tube video calculation of RL is done at Ci =50. Couldnot understand it

Seema Gupta

In the RL equation, Ci represents the highest of the initial concentrations in the experiment

article http://scielo.sld.cu/pdf/rtq/v35n1/rtq10115.pdf

page 6

You can use the optimum concentration, which showed maximum removal efficiency.