Is Citrate/Citric Acid as good as Phosphates for water softening?

amsunshineOctober 8, 2010

Just wondering if anyone has any experience/expertise to share in this regard.

Cheryl Mendelson recommends avoiding non-precipitating softeners for hard water conditions. I believe this would include borax (which I use), baking soda and washing soda.

Another poster recommended citrate or citric acid as a possible non-precipitating water softener. This is intriguing to me -- could either of these, either together, or separately, work as well as phosphates to soften laundry water?

Thanks for any help with this!

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Maybe a bad idea to add an acid to an alkaline detergent solution. I doubt it would blow up. But you'd reduce the alkalinity, and the reaction might form something you don't want in your laundry.

    Bookmark   October 8, 2010 at 8:35PM
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That might have been my thought, too. But then I noticed Tide HE has both borax and citric acid in it's "builder" ingredients. Also, the detergent I'm using now, Ecover, has both citrate and citric acid in it.

I'm stumped!

    Bookmark   October 8, 2010 at 8:38PM
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See my Oct 7 comment in the post titled, "Clothes are not so soft -- need laundry advise please" for background.

    Bookmark   October 9, 2010 at 11:07AM
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I did see your post. I have the Home Comforts book for Laundry, and I've read the section you mentioned. Wisk has enzymes, which our family needs to avoid. I didn't think 7th Gen had enzymes, but it does, and I broke out in rashes.

At any rate, I'm a little confused by Mendelson's comments -- she talks about medium hard water and then says carbonates/non-precipitating softeners would not be good to use. I assume if one has very hard water (like we do), that they would likewise not be recommended?

Also, I'm not certain how citrate/citric acid works to soften water (if it does at all). Sshriv mentioned that it is a non-precipitating softener (which might be like phosphates). I haven't been able to find a whole lot of information about this, so I was hoping to glean some wisdom from these boards.

    Bookmark   October 9, 2010 at 11:40AM
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I think there may be some confusion. Non-precipitating softeners (i.e., those who hold hardness in solution) ARE recommended for hard water. What's not recommended is PRECIPITATING softeners such as sodium carbonate, borax and baking soda. All of those cause a precipitate to form and settle on your washer and clothes.

Phosphates, citrates, and perhaps some other chemicals sequester the hardness in solution so it doesn't settle on your clothes and washer parts. Go to most major stores in the US, especially in hard water areas, and you may be able to find liquid Calgon water softener. The formula has changed over the years, so I don't know what it currently contains, but probably is no longer phosphate based. Give it a try and see if it helps.

    Bookmark   October 9, 2010 at 11:49AM
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Thanks, Sshriv...I haven't been able to find Calgon so far. But I believe it doesn't contain phosphates anyway.

I'm wondering if it would be better for me to ditch the borax I'm using and just add a little more of the Ecover, since it already contains citrate/citric acid. When I saw that Tide uses both citric acid and borax, though, that gave me pause. Tide is rated highly by CR, although it may be the enzymes that make it work better. On the other hand, maybe the borax/citric acid combo might be part of what makes Tide work well?

    Bookmark   October 9, 2010 at 12:04PM
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amsun, a little more Ecover sounds good to me. I'm going to try it also. Thank you for the tip. I have soft to medium hard water and Tide just doesn't rinse out as well for me.

    Bookmark   October 9, 2010 at 2:31PM
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patann: let me know what you think. This is all very new to me, as my frontloader is very new. I'm finding poor rinsing with whatever I've used so far, but I suspect it's the nature of the beast, er, I mean the washing machine. I'm rinsing, rinsing, rinsing, using vinegar. I'm also using less and less detergent each time. I'm down to about 2 tbsp of detergent per normal load. I may go down farther, but I think I'm dealing with residue from using too much in previous loads, so I will have to adjust as necessary.

We have very hard water (according to our city's water report). It's about 15 grains per gallon. I have no idea if the citrate/citric acid is going to be good for our situation, but I'm going to try it and see.

I'm confused, though, about something: When, exactly, is it beneficial to use borax? In soft water? I mean, if it's not recommended for medium hard to very hard water, why all the hoopla about how it softens hard water for laundry?

    Bookmark   October 9, 2010 at 2:52PM
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Hey, look what I just found:

Here is an excerpt from this article:

"In the manufacture of detergents, phosphoric acid is used to produce water softeners. Water softeners
remove Ca2+ and Mg2+ ions from hard water. If not removed, these hard-water ions react with soap and
form insoluble deposits that cling to laundry and the washing machine. Phosphates produced from
phosphoric acid are used extensively as water softeners (builders) in detergents. The most widely used
phosphorus compound in solid detergent mixtures is sodium tripolyphosphate, Na5P3O10. As a water
softener, sodium tripolyphosphate binds to Ca2+ and Mg2+, forming soluble chemical species, called
complexes or chelates. These complexes prevent the Ca2+ and Mg2+ from reacting with soap and forming

Soooo....maybe citric acid is actually a good replacement for phosphates (also an acid/chelator)?

    Bookmark   October 9, 2010 at 3:12PM
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Here is what Wikipedia has to say about Citric Acid as a water softener: Water softening

Citric acid's ability to chelate metals makes it useful in soaps and laundry detergents. By chelating the metals in hard water, it lets these cleaners produce foam and work better without need for water softening. In a similar manner, citric acid is used to regenerate the ion exchange materials used in water softeners by stripping off the accumulated metal ions as citrate complexes.The saturation point for citric acid and water is 59%. You can get citric acid in the dishwasher detergent section of your local grocery store. Look for a product called Lime Away.

    Bookmark   October 9, 2010 at 5:29PM
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Citric acid is contained in ALL the detergents that I have looked at. The detergents also contain pH adjusters to build alkalinity for cleaning. Apparently the citric acid softens independently of pH.

Adding more citric acid might not harm the cleaning ability of the detergents, because the pH adjusters usually are "buffers" which tend to keep the pH at a certain level.

Today's detergents clean very effectively and work very well in hard water, but personally, I feel that the enzymes and/or non-phosphate softeners (like citric acid) are harsher on fabrics than the old detergents were. I don't remember getting any holes in garments back in the old phosphate days.

It is hard to find detergents without enzymes. I went to 4 stores before I found Woolite Dark for HE. Tried it yesterday, and it did NOT clean as well as any of my other enzyme-containing detergents. I also bought some Bio-kleen something or other with no enzymes, just surfactants and citrus peel (probably the solvent d-limonene), but I have not tried it yet.

I think that powder formulas might rinse out more easily than the liquids. The ingredients are quite different. And Tide powder, for example, fights stains with sodium percarbonate (oxygen bleach) and has fewer enzymes. I tried Gain, which I expect to be similar to Tide, but with a better scent IMO, and I thought it cleaned and rinsed excellently at the recommended dose.

    Bookmark   October 9, 2010 at 5:30PM
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After getting some great tips from this Forum, including sshrivastava, I believe that using the exact amount of detergent recommended by that particular brand, gets clothes the cleanest and allows the water softening agents to do their job the best. I think today's detergent manufacturers formulate their detergents for hard water, just to cover all bases. I personally would add Calgon water softener if I didn't think my detergent was doing the job. Mendelson also recommends using it in the final rinse, which I haven't done yet. So far, I'm in love with Wisk. And I'm very thankful that enzymes don't bother me. Everything I've read about laundry says enzymes are necessary to clean well. But I'll still try the Ecover.

    Bookmark   October 9, 2010 at 7:40PM
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I finally found the Calgon ingredients:

Calgon liquid:

Water Diluent
Sodium Acrylic Acid/MA Copolymer Antiredeposition Agent
Citric Acid (Anhydrous) Cleaning Agent - Organic Acid
Sodum Hydroxide Cleaning Agent - Alkalinity
Fragrance Fragrance
Magnesium Nitrate Filler
Methylchloroisothiazolinone Preservative
Magnesium Chloride (Hexahydrate) Filler
Methylisothiazolinone Preservative

Calgon powder (U.S.)

Sodium Sesquicarbonate Cleaning Agent - Builder
Sulfuric acid disodium salt Filler
Sodium Citrate (Anhydrous) Cleaning Agent - Builder
Cellulose Gum Thickener
Fragrance Fragrance

Interestingly enough, the Canada Calgon powder is similar, but it substitutes STPP for the sodium citrate.

Anderssons: the Ecover has only the citrate and citric acid as softening agents. No carbonates or borax. No enzymes, either. Have you tried it?

    Bookmark   October 10, 2010 at 11:48AM
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An update on the Ecover for patann and anyone else interested:

I called their 800 number this morning to find out if there are different instructions for use in HE machines than what is on the detergent bottle. Sure enough, I was told that the amounts for HE machines is supposed to be a lot less. They said it should be approximately 1.5 ounces per "normal load" (this is 3 tbsp). My own "normal" load is probably a bit smaller than what a typical "normal" load is (I don't like overloading the machine), and I had been using about 2 tbsp for those loads, and I would up the dose to 3 tbsp for what I considered a larger load. So I was apparently on the right track -- it just suds too much if you use the amounts they recommend on the bottle (for my HE machine, at least).

So, just in case anyone is trying Ecover -- word to the wise.

    Bookmark   October 12, 2010 at 1:17PM
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sshrivastava, I would NOT recommend anyone to add LimeAway to their laundry. It contains more than just citric acid, and I think it would be too strong an acid.

Ingredients from LimeAway MSDS/Label
Chemical CAS No / Unique ID Percent
Citric acid 000077-92-9 Hydroxyacetic acid 000079-14-1 Sulfamic acid 005329-14-6

    Bookmark   October 12, 2010 at 2:52PM
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CORRECTION - I meant LEMI-SHINE, not LIME-AWAY! Thanks cryptandrus for catching the error. LEMI-SHINE should be pure citric acid crystals.

    Bookmark   October 12, 2010 at 6:51PM
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sshrivastava, I was going to ask if you meant Lemi Shine ;)

Here is a link for anyone looking for more information. Interesting info.

Here is a link that might be useful: Lemi Shine

    Bookmark   October 12, 2010 at 10:55PM
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amsunshine, what are your goals exactly? You're looking for something that will rinse more easily and not leave a residue that causes rashes? It must have no enzymes?

It seems that the main purpose of water softeners in detergents is to inactivate the mineral ions so that THEY don't inactivate the cleaning agents. It's all about cleaning power. I've done quite a bit of research now, yet I never read a WORD about rinsability of these detergents. I now have 8 or so different detergents I'm testing, and only one mentions rinsing out cleanly: it is a scent-free product for deer hunters to wash their special gear in. It says nothing about ingredients, so I have no idea if it contains anything special.

I think sshrivastava already mentioned this, but citric acid does form SOLUBLE complexes with the mineral ions. So it should rinse easily, and maybe adding some to detergent will boost cleaning and rinsing for your hard water conditions.

IIRC you recently got an HE machine. Did you have problems with rinsing or rashes with your old machine?

My mother has naturally very soft water (not softened). She has a traditional TL that uses tons of water. And she uses a high water level for fairly small loads of clothes. She uses TINY amounts of detergent, because of course in the soft water, they suds like crazy. She will only use certain detergents because she says others cause her skin rashes. I'm thinking that if SHE can't get everything to rinse out of her fabrics so as not to irritate sensitive skin, who can? Not that I want to discourage you...but it seems like a hard problem.

    Bookmark   October 20, 2010 at 1:33AM
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OK, we need a chemist to explain this, but my understanding is the

soft water = good for washing
soft water = BAD for rinsing

    Bookmark   October 20, 2010 at 9:04AM
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andersons: yes, I'm looking for something that rinses well. My new HE machine does not seem to rinse well, but I'm getting the hang of determining exactly what amount of detergent to use and amount of rinses. My problem with enzymes is mostly due to transfering wet laundry from the washer to the dryer -- if the enzymes aren't rinsed out well, my arms start breaking out in a rash. I've got that under control now, though. (I did not have a problem with my old TL -- but we also used All Free and Clear, which does not have enzymes.)

It's been a lot of trial and error. Also, I've just started using Vaska. I talked with a customer service rep who would not reveal their complete ingredient list as it is "proprietary". However, she did let me know when I asked her specifically if it contained citrate or citric acid that it does contain citric acid.

Vaska seems to be working very well for me so far -- it seems to rinse a little better than the Ecover. Don't know why.

Anyway, I'm hoping I don't jinx myself as I've only been using it for a little over a week, but I think I've found a keeper with Vaska.

    Bookmark   October 20, 2010 at 1:16PM
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As a retired chemist I can tell you that Citric acid becomes sodium citrate when it reacts with alkaline components of detergents. That form has more available citrate ions to react with calcium and magnesium than citric acid because citric acid is a weak acid and therefore is partly bound to the hydrogen ions of the acid. The acid part that is free hydrogen ions can dissolve insoluble calcium carbonate however, making the calcium available to react with the free citrate and producing carbonic acid (CO2) in the process. Thus, the combination of sodium citrate and citric acid seems like a winner for softening water. If your machine is already gunked-up with curds of carbonates then running it empty with a lot of the Lemi Shine should clean it up.

    Bookmark   October 20, 2010 at 1:25PM
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