Sandy wrote:

On Sun, 16 May 2004 23:21:33 -0400, "J. Clarke"
posted:

Sandy wrote:

On Thu, 13 May 2004 22:15:37 -0500, Unknown
posted:

On Thu, 13 May 2004 09:04:26 -0700, Larry Blanchard
wrote:

,;In article ,
says...
,; Ditto! All I can say is that the presence of ions in solution,
ionic ,; strength, does definitely affect how species in solution
react. Maybe there ,; is some physical chemistry website or ng you can
visit and ask this
,; question. I'd be interested to know, too!
,;
,;Wow! I didn't mean to start such a learned discussion :-). My
,;knowledge of chemistry is limited to making various explosive
,;compounds, learned long ago in my juvenile days. And lately, I
,;think I've forgotten most of that - CRS seting in :-).
,;
,;But what I meant by "ask a chemist" is that a friend of mine who
,;is a chemist said that the vinegar and salt combined to form a
,;weak hydrochloric acid. I took his word for it.

You shouldn't have as he was wrong.

Vinegar is approximately 5% acetic acid plus some other goodies to
provide some taste. The hydrogen ion concentration is not sufficient
to react with metallic iron and therein lies one of the keys to the
process. The other key is the fact that chloride ions form a stable
complex with iron ions in solution. The iron chloride complex is
strong enough so that iron oxide will dissolve and form that complex.
Since there is no oxidant strong enough to react with iron metal the
net result is that the iron oxide goes into solution as the chloride
but the iron metal does not react.

It is essential that the solution be kept oxygen free or the metal
will dissolve. This is particularly noticeable if you allow the metal
to be "derusted" to stick out of the solution into air e.g. you will
find that there has been a dissolution of iron metal at the air liquid
interface.

The role of the acetic acid is to keep the solution acidic enough to
prevent the precipitation of iron oxide but low enough so that iron
metal does not react with hydrogen ions. It is the high concentration
of chloride that removes the rust not a "weak hydrochloric acid".

How so exactly?
Iron acetate is surely soluble enough?

If one used a concentrated salt solution without the acetic acid then
one would get a preciptate of hydrous iron oxide at the surface. This
would slow the reaction to a crawl.

Um, surely without the hydrogen ions, you are not going to get any
dissolution of anything in the first place. All you need is an anion
along with the H+ that does not form an insoluble precipitate with the
resulting iron ions.

A weak acid such as acetic acid allows one to put a lot of acid in the
solution but maintain a relatively low hydrogen concentration.

Yep, that's what "weak" means wrt acids and bases.

The solution if kept covered can be used repeatedly until the amount
of dissolved iron reaches a point where the hydrous oxide begins to
precipitate.

Where you have infact neutralised all the acetic acid present.

If the used solutions are left open to the air then it
will accumulate ferric chloride as a result of air oxidation.

No, it will remain a solution of iron ions, acetate ions, sodium ions
and chloride ions. The iron ions will slowly precipitate to iron
hydroxide complexes as the final H+ ions are used up. No?

That
ferric chloride is an oxidizing agent strong enough to react with iron
metal which is the reason one gets an "etch line" at the liquid
surface.

Yes, if what you had was ferric chloride. You don't. You have a
neutral solution of the ions I just mentioned, surely.

You keep asking this question over and over.

Perhaps because I've not seen a satisfactory answer yet, and the
person who wrote that article quoted, has asked to state the query
again?

First, if you have ions they
are not "neutral".

Huh? Sodium chloride solution is neutral.

By definition an ion is electrically charged, hence it
is reactive.

Got nothing to do with chemical neutrality, sorry.

The solution is neutral because for each cation there is a
matching anion with the opposite charge, but the ions themselves are not
neutral at all.

I never said ions were neutral -- I was talking about the solution.
The solution MUST be electrically neutral, but chemical neutrality has
to do with balance between H+ and OH- in the solution.

"The solution" is not what reacts with the rust. What reacts with the rust
is individual ions within that solution.

Second, chlorine is one of the most reactive of all
elements,

There is NO elemental chorine involved, sorry.

So what is a chlorine ion floating around with its electrical charge exposed
if not "elemental chlorine"? What comes in contact with the rust is not
sodium and chlorine bound, it's individual sodium ions and individual
chlorine ions.

hence any reaction involving chlorine will proceed at a higher
rate than one involving acetate.

See above. The chloride ion is arguably more stable than the acetate
ion.

I thought we were talking chemistry here, not physics. A monatomic ion is
not "stable" or "unstable" chemically--that's a property of a compound.

The end result is that by putting some
chlorine ions in the solution you end up with a faster reaction.

Sorry, your premises are wrong so your conclusion is not sound.

No, your understanding of what constitutes an ion is so wrong that you can't
follow the argument.

--
--John
Reply to jclarke at ae tee tee global dot net
(was jclarke at eye bee em dot net)