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Antifreeze Smells Like Ammonia

01/14/2017 1:05 PM

Strange effect me and my brother are experiencing with both of our boilers now.

About two years ago I picked up around 600 gallons of good clean antifreeze from the place I worked for due to company policy not allowing for the reuse of it if a engine it was in ever had to be taken apart for service.

Super deal being it was the good high end stuff with all the proper anti corrosion inhibitors and everything else added but here's the odd thing about it. It sat in tote tanks outside for around a year before being used in our boiler systems and now it has a strong ammonia smell to it when it heats up.

Make your eyes burn bad fumes from the boiler vents when it gets hot. As tested it boils at around 220*F and survived -27*F nights without freezing (minor slush effects that morning in my tote tank) suggesting it has a ~ 40 - 45% mix ratio which for what we are using it for is plenty good.

Any ideas about whats causing it? Did one or more of the additives start to breakdown due to light exposure?

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#1

Re: Antifreeze smells like ammonia.

01/14/2017 1:23 PM

Light exposure?

Is it in glass jugs?

You might have some analyzed.

I've never heard of this myself but it doesn't sound right.

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#2

Re: Antifreeze smells like ammonia.

01/14/2017 1:34 PM

It's possible you have the remnants of some chemical flush ingredients in the antifreeze...Sodium Citrate Na3C6H5O7 is common...this may have formed some NH3 over time....

https://www.bobistheoilguy.com/forums/ubbthreads.php?ubb=showflat&Number=614937

"Ammonia may be conveniently deodorized by reacting it with either sodium bicarbonate or acetic acid. Both of these reactions form an odourless ammonium salt."

https://en.wikipedia.org/wiki/Ammonia

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#13
In reply to #2

Re: Antifreeze smells like ammonia.

01/14/2017 3:19 PM

<...this may have formed some NH3 over time...> Fascinating. So where did the nitrogen come from?

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#14
In reply to #13

Re: Antifreeze smells like ammonia.

01/14/2017 3:24 PM

Clearly the nitrogen is due to beta decay of all those carbon isotopes. Better check for radioactivity whilst we're at it. May I suggest DU-shielding that boiler?

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#16
In reply to #14

Re: Antifreeze smells like ammonia.

01/14/2017 3:56 PM

haha...ooops

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#21
In reply to #14

Re: Antifreeze smells like ammonia.

01/14/2017 9:10 PM

Sure. I was going to build from DU anyway just to burn up my multi ton stockpile of DU sheeting but the stuff welds like crap with 6013 rods so I went with high carbon steel instead out of laziness.

Laziness is my primary motivator for doing anything you should know.

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#25
In reply to #21

Re: Antifreeze smells like ammonia.

01/14/2017 10:06 PM

By "welds like crap" it catches fire you mean? (which it can) We didn't weld it but we did evaluate about 2 kg of it to block 'hard' (250keV-1MeV) X-rays from damaging control electronics in a product years ago. Much more effective than lead for the same thickness.

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#15
In reply to #13

Re: Antifreeze smells like ammonia.

01/14/2017 3:50 PM

By volume, dry air contains 78.09% nitrogen, 20.95%oxygen, 0.93% argon, 0.04% carbon dioxide, and small amounts of other gases.

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#18
In reply to #15

Re: Antifreeze smells like ammonia.

01/14/2017 4:11 PM

If his antifreeze was exposed to air for that long, he's got other problems. Ethylene glycol can oxidise to five organic acids (formic, oxalic, glycolic, glyoxalic and acetic acid). Propylene glycol exposed to air and heat oxidises to lactic acid. If the additive to buffer against this is a nitrite, there's your nitrogen source.

I would simply contact the product's mfr, tell them the problem, ask them what's going on and what to do about it.

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#22
In reply to #18

Re: Antifreeze smells like ammonia.

01/14/2017 9:16 PM

The totes have sealed lids on them so I would have some doubts on it being excessive air exposure. Possible but I use the same totes for hauling used oil and I have never had one leak out the lid ever so I trust the antifreeze tote seals as well.

I did however work on a tractor today that I put a bunch of the antifreeze in a year or so ago and I got nothing for odd smells from it when I opened the radiator cap. Same with the 2.5 gallon jugs of it I gave my dad last summer as well. No discernible ammonia smell there either.

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#23
In reply to #22

Re: Antifreeze smells like ammonia.

01/14/2017 9:38 PM

Interesting, and possibly a clue. Earlier you said "And yes, the totes do have the residual smell too. Not really noticeable when cold though but it is there and yes we have about 300 gallons of the stuff left over yet," but the jugs and radiator do not have this smell.

Are the jugs and radiator full, whereas the totes may contain air even though they're sealed, because they're no longer full? What of the boiler? How much air is in that? I'm wondering if something in the air-exposed antifreeze has decomposed. Heat would no doubt would accelerate this process.

Also, if you google search "antifreeze ammonia smell odor," you'll see that others have experienced this phenom also, though I've yet to see anything conclusive as to the cause.

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#26
In reply to #23

Re: Antifreeze smells like ammonia.

01/14/2017 10:36 PM

Jugs and radiator were full or close to it.

The boiler is an open system and can breath as it needs to so that's possible. It just seems odd that other who run open type boiler systems with antifreeze don't have similar issues.

YEa I 've dug through other internet talks about at and as you I didn't find anything useful either. That's why I asked here.

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#34
In reply to #26

Re: Antifreeze smells like ammonia.

01/17/2017 5:48 AM

By open system, do you mean a vented system with header tank, as opposed to a sealed system with expansion vessel? If so presumably the smell is at the header tank, as that's the only place it could be released. Once the system is up and running there should be negligible gas flow from the vent.

Maybe the ammonia is being produced in the header tank, as that's where it has contact with the air, as others have suggested. It might be worth taking a sample, say a couple of pints, from a drain point, and see if that smells. Doesn't cure it, but might pin down the source.

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#24
In reply to #22

Re: Antifreeze smells like ammonia.

01/14/2017 9:40 PM

Is it possible you are exceeding the maximum temperature for this solution?

I found an additive in most antifreeze called tolytriazole C7H7N3....this could be reacting with the other chemicals to produce some ammonia....

https://en.wikipedia.org/wiki/Antifreeze

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#30
In reply to #15

Re: Antifreeze smells like ammonia.

01/16/2017 4:15 AM

As a learning exercise for the forum, please detail the reaction with atmospheric nitrogen that has ammonia as a product.

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#3

Re: Antifreeze smells like ammonia.

01/14/2017 1:34 PM

Do the totes still have some in them? Do they smell like ammonia also?

Bacteria can decompose the stuff. Check inside the totes for signs of bacterial growth.

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#4

Re: Antifreeze smells like ammonia.

01/14/2017 2:04 PM

The totes are clean and the same ones the new antifreeze the company used normally came in.

The only contamination I have seen is the slight oily residue that got picked up from the transfer hoses or whatever when it got dumped out of the engines it came from at the time. Surface residue.

As for chemical analysis we don't want to spend much if anything to find out exactly what it is. It's just annoying to go into our boiler rooms and get hit with wicked stink if the systems are running hot.

If it could be cleaned up simply and easily without affecting overall antifreeze performance and characteristics that would be good but if not we are adding external boiler venting lines to put it outside.

Mostly I'm just curious as to if someone knows the more scientific explanation for the smell other than 'weird shit happens sometimes.'.

And yes, the totes do have the residual smell too. Not really noticeable when cold though but it is there and yes we have about 300 gallons of the stuff left over yet.

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#7
In reply to #4

Re: Antifreeze smells like ammonia.

01/14/2017 2:15 PM

If your boiler system contains any copper, zinc, brass, or similar materials exposed directly to the coolant, any ammonia present will corrode it. If this is the case I'd flush the system.

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#9
In reply to #7

Re: Antifreeze smells like ammonia.

01/14/2017 2:21 PM

Since I got it I have been using it in all of our farm equipment and vehicles and so far nothing had shown up in the last near two years.

Same with the boilers, Copper and brass Pex fittings and water to air heat exchangers and so far we have had linesets open a few times for system improvements and add ons and nothing has shown any signs of corrosion on any of the copper or brass components.

If it's happening it happening so slow that it's not a discernible effect after several months to near 2 years of exposure.

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#11
In reply to #9

Re: Antifreeze smells like ammonia.

01/14/2017 2:29 PM

Is it also possible the ammonia concentration is increasing over time? I mean, you didn't notice it at first, right? But now you do? If this is the case, the corrosion you've seen thus far may not be a reliable indicator of potential problems you may have with it in the future.

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#17
In reply to #4

Re: Antifreeze smells like ammonia.

01/14/2017 4:03 PM

Maybe one of the cows took a wiz when you weren't looking....

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#5

Re: Antifreeze smells like ammonia.

01/14/2017 2:10 PM

Maybe the company you worked for "denatured" it to keep it from being reused or sold.

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#8
In reply to #5

Re: Antifreeze smells like ammonia.

01/14/2017 2:16 PM

I was buddies with the mechanics and they didn't do anything to it. They knew I wanted some so they made a point to save it for me. It was clean stuff when I got it.

At least half of it was in one frac pump engine for maybe 2 - 3 months before it got dumped out. The rest was maybe a year old at most and came from other pump engine and company vehicle engines.

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#37
In reply to #8

Re: Antifreeze smells like ammonia.

01/19/2017 2:25 AM

They may not have done anything, but the anti freeze may have been "denatured" prior to their saving it for you.

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#6

Re: Antifreeze smells like ammonia.

01/14/2017 2:14 PM

Could the antifreeze have been used in an ammonia-based chiller application instead of actually in engines?

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#10

Re: Antifreeze smells like ammonia.

01/14/2017 2:21 PM

Contact the product-manufacturer's tech support people and ask about it; downside of long-term storage and possible reactions with the container material, decomposition products, etc. Ammonia may be one of them. Their chemists would know these things.

Also, is ammonia used anywhere in the system from which this came and possibly could have been introduced that way?

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#19
In reply to #10

Re: Antifreeze smells like ammonia.

01/14/2017 9:05 PM

Unfortunately I dont have the manufactures name any more. The labeling on the tote faded to unreadable off white some time ago so i have no readable name to work with.

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#12

Re: Antifreeze smells like ammonia.

01/14/2017 3:06 PM

It might be a good idea to take a ph reading....

..."Control of pH between 8 and 10 is important to minimize corrosion and glycol degradation."...

..." Adjustments can be made by using a 50% solution of sodium hydroxide or potassium hydroxide if the pH is between 7.0 and 8.0. Any fluid with a pH below 7.0 should be replaced."...

ref link

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#20
In reply to #12

Re: Antifreeze smells like ammonia.

01/14/2017 9:06 PM

Unfortunately I don't do chemistry as a hobby and thusly have no PH testing gear at all.

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#27
In reply to #20

Re: Antifreeze smells like ammonia.

01/14/2017 11:29 PM

here ya go

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#28
In reply to #27

Re: Antifreeze smells like ammonia.

01/15/2017 12:32 AM
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#29

Re: Antifreeze smells like ammonia.

01/15/2017 10:01 AM

I'll dig into it a bit more when I can. I has me curious so I will probably do a bit of experimenting to see what I can come up with that may improve things.

I'm curious about the PH and if a baking soda will precipitate anything out that won't drastically affect the freeze protection aspects.

I'm also curious to see if just boiling it a for a bit will drive the ammonia out to any effect since heat obviously drives up the outgassing rates.

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#33
In reply to #29

Re: Antifreeze smells like ammonia.

01/16/2017 7:18 PM
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#31

Re: Antifreeze Smells Like Ammonia

01/16/2017 1:37 PM

Could be something biological growing in it. I found this...

http://www.eng-tips.com/viewthread.cfm?qid=257737

cat cooling systems

2 thread71-257737

mechanic6 (Automotive) (OP) 28 Oct 09 22:49 we have several cat gensets,3500 series and 3600 series.in the last few years we have had to replace 3 rads and 1 jacket water aftercooler core due to corrosion.
the antifreeze is as per the cat recommendation and is changed out every 2nd year(usually).
we monitor the additive levels but still have this problem.
we do not have this problem with our detroit disel or mitsubishi diesel gensets.
ideas???
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catserveng (Electrical)29 Oct 09 22:39 What kind of antifreeze are you using? Should be an HD antifeeze with a diesel engine inhibitor package, low silicate and nil phosphate. How about the water you're using when you refill, does it meet the CAT spec? How often are you adding SCA (corrosion inhibitor)? What inhibitor are you using? How often do you test and how? Take a sample of coolant, let it cool and give a sniff test, if it has an ammonia smell you need to check for active biological growth and may need to add a biocide, especially on the 3600 engines.

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#32
In reply to #31

Re: Antifreeze Smells Like Ammonia

01/16/2017 7:11 PM

Interesting. I wonder what biological based contamination I could possibly have that manages to live in a boiler and feed off antifreeze and or its possible additives that regularly hits 195 - 200+ F water temps every burner firing cycle?

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#35
In reply to #32

Re: Antifreeze Smells Like Ammonia

01/17/2017 12:10 PM

I don't know but I wouldn't wanna tick it off....

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#36

Re: Antifreeze Smells Like Ammonia

01/18/2017 10:14 PM

There are flushing compounds (CITRO-CLEEN) that use ammoniated citric acid (46% by volume) as the active ingredient, so the ammonia is already there. Your "clean" antifreeze was probably used in descaling a boiler or process machinery, and judging from the quantity and strong odor, you probably got the "first flush" batch from a relatively clean system; hence it looked like "pure" antifreeze.

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#38

Re: Antifreeze Smells Like Ammonia

03/20/2017 1:07 PM

For a follow up. My brothers copper heat exchangers corroded though. His PH test strips were off the charts that went to 11.

Mine read around 9.5 (normal expected value for ethylene glycol antifreeze with corrosion inhibitors) and one sample I took I did a boil off test with it and it cleaned up fine. After about minute of light boiling the smell disappeared.

I had my boiler lines out for a size upgrade for the house feed circuit and none of the brass fittings showed any signs of corrosion or pitting.

Next best guess to get rid of my issue is to try giving the system a good hard boil and see what happens from there.

For my brother, he has to replace all his copper and brass based components and do a full systems flush now.

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#39
In reply to #38

Re: Antifreeze Smells Like Ammonia

03/20/2017 1:23 PM

Did your brother's system smell of ammonia? Because ammonia attacks copper quite readily and that could be why it was corroded through. There's lots of copper in a CH system and I think I'd be a bit nervous if I could smell ammonia. Might be worth doing a test, drop some copper pipe in a sample of system water.

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#40
In reply to #39

Re: Antifreeze Smells Like Ammonia

03/22/2017 6:15 AM

Did you not read the title or one sentence of the whole of the thread?

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#41
In reply to #40

Re: Antifreeze Smells Like Ammonia

03/22/2017 6:53 AM

I did once but I'd forgotten and didn't re-check. Terrible, isn't it?

I still think the ammonia could have rotted through your bro's heat exchanger. There'll be more free ammonia at his higher pH, but can't guess why it's higher.

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