Solvated electrons in ammonia solution

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    Ammonia Electrons
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Discussion Overview

The discussion revolves around the phenomenon of solvated electrons in ammonia solutions, particularly focusing on the blue color observed when alkali and alkaline Earth metals are dissolved. Participants explore the reasons behind this color change, the behavior of solvated electrons, and the differences between ammonia and water as solvents.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • Some participants propose that the blue color is due to the dissolution of electrons common to all alkali and alkaline Earth metals.
  • Others argue that the behavior of these metals is similar because they have low ionization energy, resulting in small cations that attract polar molecules.
  • A participant questions the difference between "ammonia solution" and "liquid ammonia solution," suggesting that the terminology may affect the understanding of the reactions involved.
  • There is a discussion about why solvated electrons in ammonia do not react in the same way as those in water, with some suggesting that solvent reorganization may be energetically costly.
  • One participant mentions that solvated electrons in ammonia can react to produce hydrogen, forming sodium amide under certain conditions, but questions about the speed of this reaction remain.
  • Another participant raises a point about the paramagnetic nature of blue ammonia-alkali metal solutions compared to the diamagnetic properties of bronze solutions.
  • Concerns about the practicality of using ammonia gas instead of liquid ammonia for experiments are discussed, including the unpleasant odor and potential safety issues.

Areas of Agreement / Disagreement

Participants express various viewpoints, and there is no clear consensus on the reasons behind the blue color or the behavior of solvated electrons in ammonia versus water. Multiple competing views remain regarding the reactions and properties of solvated electrons.

Contextual Notes

Participants note limitations in understanding the kinetics of reactions involving solvated electrons and the conditions under which these reactions occur. The discussion also highlights the need for clarity in terminology related to ammonia solutions.

aim1732
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Ammonia solution turns blue when alkali and alkaline Earth metals are dissolved in it. Why is the blue colour common to all? Is it because of the dissolution of electrons that is common in all cases?
 
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Yes - they all behave similarly.

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No, that was the answer.

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Sorry, but what I meant was why do they all behave similarly?
 
They have similar characteristic - low ionisation energy and after electron(s) are removed you are left with small cation, that easily attracts polar molecules. Not to mention fact that these small cations have filled all other orbitals, so there is no further fancy chemistry possible as is in the case of transition metals.

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methods
 
Thanks.
 
aim1732 said:
Ammonia solution turns blue when alkali and alkaline Earth metals are dissolved in it. Why is the blue colour common to all? Is it because of the dissolution of electrons that is common in all cases?
Do you mean liquid ammonia, or a solution of alcali metals in ammonia, not "ammonia solutions".
The reason is what Borek wrote: all those metals release an electron and the blue color is due to this ammonia-solvated electron, so the nature of the metal is not important anylonger.
 
I meant liquid ammonia solution but pardon me, what's the difference?
 
  • #10
Ammonia solutions implies ammonia dissolved in water. What happens when you mix alkali metals with water?

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methods
 
  • #11
aim1732 said:
I meant liquid ammonia solution but pardon me, what's the difference?
You wrote:
"Ammonia solution turns blue when alkali and alkaline Earth metals are dissolved in it".
It seems that you start from ammonia solutions of something and then you add the metals. I would instead have written: "ammonia solutions of alkali and alkaline Earth metals..."
 
  • #12
Here's a a question to which I've been wondering the answer: why do electrons solvated in ammonia not react, whereas electrons solvated in water, even under basic conditions, DO react to form H2?
 
  • #13
jwiens said:
Here's a a question to which I've been wondering the answer: why do electrons solvated in ammonia not react, whereas electrons solvated in water, even under basic conditions, DO react to form H2?

Electrons solvated in ammonia DO react to produce hydrogen. It forms sodium amide. It does it slowly if the ammonia is extremely cold, however. Most 1 electron reductions (the most common use of sodium in ammonia) occur much more rapidly than the reaction of the electron with a hydrogen on ammonia at those temperatures. I use the stuff at -78oC when I have a need for it. And I generate it just before I need it. It has no shelf life.
 
  • #14
chemisttree said:
Electrons solvated in ammonia DO react to produce hydrogen. It forms sodium amide. It does it slowly if the ammonia is extremely cold, however.

Are you saying that the reaction is reasonably fast under ambient conditions? If that were the case, then the blue color would start to disappear, right? I haven't dealt with the stuff.

Barring the reaction with ammonia itself, why don't the solvated electrons react with each other to form H2, as in water (this was actually the question I was asking)? Is solvent reorganization too energetically costly (during reaction) in ammonia? I wonder if I can't find the solvation enthalpy for electrons in ammonia. . .

What kind of shelf life are we talking? Minutes?
 
  • #15
The solvation process of the electron both in water and in ammonia has been the topic of extensive research with femtosecond spectroscopy in the last decades. For example, the first stages of solvation are known as "wet electron".
 
  • #16
jwiens said:
... why don't the solvated electrons react with each other to form H2, as in water (this was actually the question I was asking)?
What does it mean? Electrons (solvated) reacting with each other? In case, electrons react with the solvent.
 
  • #17
jwiens said:
Are you saying that the reaction is reasonably fast under ambient conditions? If that were the case, then the blue color would start to disappear, right? I haven't dealt with the stuff.

Barring the reaction with ammonia itself, why don't the solvated electrons react with each other to form H2, as in water (this was actually the question I was asking)? Is solvent reorganization too energetically costly (during reaction) in ammonia? I wonder if I can't find the solvation enthalpy for electrons in ammonia. . .

What kind of shelf life are we talking? Minutes?

At ambient temperature ammonia is a gas of course. It boils at something like -33C so solutions of sodium in ammonia are always pretty cold. The reaction of the sodium with the hydrogens of ammonia is exactly how sodium amide is made. I don't know the kinetics but whenever I use sodium in ammonia to reduce something, I always use it in a bit of excess to account for its decomposition to sodium amide, reaction with stuff on the glassware, stuff in the ammonia, stuff in my reaction not leading to product, etc... Just how much excess is dependent on the rate of reaction as well. If something were difficult to reduce, I would add a little more excess by trial and error.

Of course I've never done one of these reactions on a large scale... usually 50-100 mg scale.
 
  • #18
There's something else that bothers me. The blue ammonia-alkali metal solutions are paramagnetic whereas the bronze ones are diamagnetic. Can anybody explain?
Thanks in advance.
 
  • #19
I have a quick question someone, anyone...Is it possible for one to use ammonia gas, instead of liquid (i know about condensing the gas into dry ice container below temp -33 but the stuff smells awful! i live and share an apartment complex :( )? Let's say one was to put the ammonia gas into some kind of liquid absorbent it is soluble with and adding in the lithium to the solvent?
 
  • #20
No matter if you will work with liquid or gaseous ammonia, it will stink enough for your neighbors to call the police.
 
  • #21
bettlejuice said:
I have a quick question someone, anyone...Is it possible for one to use ammonia gas, instead of liquid (i know about condensing the gas into dry ice container below temp -33 but the stuff smells awful! i live and share an apartment complex :( )? Let's say one was to put the ammonia gas into some kind of liquid absorbent it is soluble with and adding in the lithium to the solvent?

I don't even want to know why you want to perform a Birch reduction in your apartment.

No prizes for guessing, though.
 

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