Biopowered - vegetable oil and biodiesel forum

Biodiesel => Chemistry and process => Topic started by: DavidA on November 16, 2021, 06:57:38 PM

Title: The Blues.
Post by: DavidA on November 16, 2021, 06:57:38 PM
No, not the musical variety.

I keep noticing that the names Bromophenol Blue and Bromothymol Blue are used a lot. But are they the same  (I have both).
I am assuming that the correct one for soap testing is Bromophenol Blue.

Dave.
Title: Re: The Blues.
Post by: WesleyB on November 16, 2021, 07:47:43 PM
From a brief internet search Bromophenol Blue under goes a color change in the pH range 3.0-4.6 .  Bromothymol Blue under goes a color change in the pH range 6.0-7.6 .  Soap is basic , above pH 7 .  Titrating soap with strong dilute acid produces free fatty acids and inorganic salt , which should be acidic . Acidic pH is less than 7 .  So a pH indicator to use in testing soap content would be bromothymol blue , I think .  If I recall correctly the sample is dissolved in dry isopropyl alcohol then dilute hydrochloric acid is added with stirring till the Bromothymol blue changes color , from basic to acidic .  Then the quantity of hydrochoric acid added to acidify the alcohol is calculated .  An equivalent amount of soap expressed in moles is present . The mass of the soap present can be calculated from the average molecular weight of the soap times the number of moles of the soap in the sample .  With more calculation knowing the mass of soap present , I could get parts per thousand or parts per million in a litre of biodiesel .  It has been some time since I did this titration and calculations for it . 
Title: Re: The Blues.
Post by: countrypaul on November 17, 2021, 09:32:06 AM
Bromophenol blue is the usual indicator used I believe.

This Wiki article gives a detailed explanation: http://biopowered.co.uk/wiki/Soap_tests#Titrated_soap_test
Title: Re: The Blues.
Post by: DavidA on November 17, 2021, 11:01:17 AM
Thanks for the responses.

I was just wondering what the opinion of the folks on the ground was.

I will be using the Bromophenol Blue.  Can't recall why I acquired the other one.
Title: Re: The Blues.
Post by: dgs on November 17, 2021, 01:47:45 PM
I've used both and have both, there is very little difference. The soap test if done properly is about the quickest and most accurate of all the 'shed' tests. Make sure you blank off the ipa. With an accurate titration you can get a result of +/- 5ppm.
Title: Re: The Blues.
Post by: DavidA on November 17, 2021, 07:08:11 PM
dgs,

So you're saying that the quite different Ph switching points doesn't matter ?

Bromophenol Blue  below 3.5 yellow, above 4.6 blue

Bromothymol Blue  below 6.0 yellow, above 7.6 blue.
Title: Re: The Blues.
Post by: dgs on November 18, 2021, 12:38:10 PM
dgs,

So you're saying that the quite different Ph switching points doesn't matter ?

Bromophenol Blue  below 3.5 yellow, above 4.6 blue

Bromothymol Blue  below 6.0 yellow, above 7.6 blue.

Not quite. At low ppm levels, lets say around the K spec level of 66ppm there will be little difference as with a low titration the pH will soon alter. However at higher levels the Potassium Chloride salt formed will have the effect of buffering the solution, so the different end point pH's will have an effect on the test result.

Having said that we usually don't titrate at very high soap levels, there is no point, making the second example a little meaningless.

Hope you understand all that dribble.
Title: Re: The Blues.
Post by: countrypaul on November 18, 2021, 06:41:14 PM
Since you have both indicators, try carrying out the titrations on several different samples (with little soap though to lots of soap) using both indicators and see how different the results are. With nearly all titrations there is a difference between the endpoint (where the indicator changes) and the equivalence point (where the neutralisation in this case finishes) however the difference is normally small enough to be ignored.

The buffering is due to the mixture of a weak acid strong base (or vice versa) where the weak acid is not fully disassociated so adding a little more strong base has little effect on the pH as it results in the undisassociated acid being neutralised, but because it had no free protons it does not affect the pH. Adding a little more strong acid also has little effect as it will convert the weak acid/strong base salt to weak acid plus strong base/strong acid salt. Once the conversion is nealy complete the pH changes rapidly.

Here is a better explanation: https://en.wikipedia.org/wiki/Buffer_solution
Title: Re: The Blues.
Post by: DavidA on November 18, 2021, 07:30:24 PM
Thanks for both responses.

I intend to do a series of tests using both indicators with the same batch oil oil and the same (new) IPA.  I won't blank the IPA as that may add another variable to the test.

I'll let you know how it all turns out.

Dave.
Title: Re: The Blues.
Post by: countrypaul on November 18, 2021, 11:18:02 PM
Thanks for both responses.

I intend to do a series of tests using both indicators with the same batch oil oil and the same (new) IPA.  I won't blank the IPA as that may add another variable to the test.

I'll let you know how it all turns out.

Dave.

You should blank the IPA otherwise you are introducing another variable and none of your results will therefore be reliable. Adding an almost random amount of acid especially a weak organic acid will act as a buffer as discussed earlier.

Using the same batch of oil (do you mean bio?) will only give you one data point, ideally you want several different data points so differing titrations on each sample. You should carry out 3 titratons for each sample with each indicator - this will help check you method of tritrating and give you an idea of accuracy.
Title: Re: The Blues.
Post by: dgs on November 19, 2021, 09:51:40 AM
Just a couple of things here Dave. I agree with Paul that the ipa should be blanked, ipa tends to go acidic with age and as you are titrating from base to acidic you have to make the ipa slightly alkaline (basic) in order to blank it. I usually do this by adding a very small amount of sample (depending on variables one drop is sometimes sufficient)


Also as the result should be stated on a w/w basis it is more accurate to use an 11ml sample as this is far closer to the 10gms we should actually use.

It's good that a newcomer on this forum is doing some experimental work, a technical post, WOW its like starting all over again!

PS use a 1ml pipette to titrate with and make sure you use the same volume of ipa each time.
Title: Re: The Blues.
Post by: DavidA on November 19, 2021, 12:07:15 PM
Thanks for the comments.

I usually blank the IPA for my NaOH calculations. But assumed that as I was using the same batch of IPA for all the tests it wouldn't matter. On reflection It will be better to do so or I won't know how much of the titration solution was used on the bio and how much on the IPA.

I have been watching Graydon Blair's Video on this. Any comments on it ?

I really need to do two sets of tests. One using the old IPA and one using the new stuff I got from Dave.

And three tests for each to get an average.

I'll report back when it's done. (at 20C, naturally).

Paul, Yes, I do mean Bio. Sorry about that.


P.s.
Actually it's four sets. Two for each indicator.
Title: Re: The Blues.
Post by: nigelb on November 21, 2021, 01:38:22 AM
Always blank your IPA.  Uncle H a few years back had issues with soap testing. Turned out that all of his testing problems, following my intervention, were due to the IPA he'd bought off the interweb.

If you are having issues with testing or production...question everything.
Title: Re: The Blues.
Post by: DavidA on November 22, 2021, 01:45:07 PM
I intend to.

I reckon the best way to ensure consistency over a set of tests will be to measure out enough IPA to do the whole lot and then blank it.  Drawing off as much as I need for each test.

That way I will know that at least the IPA is all the same.

The Bromophenol blue I was waiting for has just arrived, so I can get on with the testing.
Title: Re: The Blues.
Post by: DavidA on November 24, 2021, 05:49:08 PM
Well, something happened that I wasn't expecting; or rather it didn't happen.

I put 100mL IPA (the good stuff, from dgs) into a beaker, At 20C.

Then added in ten drops of Bromophenol Blue.

And nothing happened. It didn't turn blue as expected. Just stayed clear.

I spent a long time and a lot of IPA on this problem but haven't yet come to any conclusion why it didn't go either blue or even yellow.

I'm still working on this. But am going to have to get some more IPA soon.

Life was so easy before I started on this soap thing.

p.s.  The same happened using Bromothymol Blue.

Note that I haven't got as far as blanking or adding oil  yet.
Title: Re: The Blues.
Post by: nigelb on November 24, 2021, 06:48:48 PM
Try using less IPA. In my soap test tutorials I only used 50ml. 100ml is such a waste. Its only there as a carrier. Also what % is your bromophenol blue?
Title: Re: The Blues.
Post by: DavidA on November 24, 2021, 08:09:55 PM
0.04% as is the Bromothymol blue.

I agree it is very wasteful, but I was following Graydon Blair's instructions as shown in the wiki.

I wasn't sure if it was necessary to use so much to get a quantitative measurement of the soap from the amount of 0.01N HCL used in the titration.

I would be much happier using, say, 25 mL if it will yield the same result.

IPA isn't cheap.
Title: Re: The Blues.
Post by: nigelb on November 24, 2021, 08:37:51 PM
You need the bromophenol blue to be 0.4%. Thats why its not making a jot of difference to a colour change to the IPA
Title: Re: The Blues.
Post by: DavidA on November 24, 2021, 08:56:37 PM
So, ten times stronger.



Time to go internet shopping again.

Thanks for that
Title: Re: The Blues.
Post by: nigelb on November 24, 2021, 09:21:46 PM
Its all in the wiki under soap testing.
Title: Re: The Blues.
Post by: DavidA on November 24, 2021, 09:28:21 PM
Where do you buy your 0.4% Bromophenol blue ?
Title: Re: The Blues.
Post by: nigelb on November 24, 2021, 10:35:26 PM
I used to buy it from a lab supply buisness in Atherstone. Not sure it's still there. I used to deal in soap testing...but i've only got 30ml left.
Title: Re: The Blues.
Post by: countrypaul on November 24, 2021, 11:32:25 PM
Try the obvious first, use 10 times as much indicator as you have tried. Given the small overall amount in 100ml of ipa using 10 times as much should not have any adverse effect.
Title: Re: The Blues.
Post by: DavidA on November 25, 2021, 01:13:12 PM
0.4% Bromophenol seems very expensive (and hard to come by).  I may try a compromise and get some 0.1%. It's cheaper may work.

For the time being I'm going to run a few tests using Bromothymol blue as I have about 500mL of that.

I'll hold back some of the bio I use so I can compare the results with the Bromophenol blue when I get some.

A quick tip.
I found that the 1 mL syringes you can get from the pharmacists will, if you cut of the little 'wings' at the top, fit neatly into a two mL pipette pump. And they are only 50 Pence each.
Title: Re: The Blues.
Post by: DavidA on December 02, 2021, 04:39:20 PM
A quick question.

How much soap would you expect to find in unwashed bio ?

My test sample shows (apparently), 100 % conversion; 1 litre of oil in, 1 Litre of bio out.

The byproducts equal the total Methanol I used.

I ask this because, as you know, I am doing some soap tests.

I have just watched the video recommended by the people who supplied my soap kit (Intelli-ink), and the guy there used 11 mL of 0.01n HCL to get a result of 3344 ppm.

Is this what I should expect ?

And would washing greatly reduce this figure to something nearer the ASTM acceptable 41 ppm ?

I has me wondering because I never used to do soap tests on my fuel, and it didn't appear to do any damage.
Title: Re: The Blues.
Post by: nigelb on December 02, 2021, 07:52:41 PM
Unwashed raw bio from my experiments can be as high as 13000pm.
Doing a post reaction wash will typically reduce it to 1300ppm.
There is some anacdotil info on testing on the vod.

Testing raw bio can take a heavy hit on your indicator and lab grade HCL unless you reduce the sample size and then multiply the result by the same factor.
Title: Re: The Blues.
Post by: DavidA on December 02, 2021, 08:11:22 PM
A very heavy hit indeed.

Looks as if it will soon be time to shift to doing micro-samples.
Title: Re: The Blues.
Post by: DavidA on December 05, 2021, 04:40:08 PM
Anyway, I got a result.
Here is the process.

10/90 test on bio showed no discernible drop out overnight.

Washed bio.
100 mL bio + 100 mL lukewarm water. Used Tilly method.

After seven wash cycles both water and bio passed the 'newspaper' test.

700 mL water used in total.

Soap test.

50 mL good IPA in 250 mL beaker on stirring table.

Blanking.  Three drops 0.1% Bromophenol Blue indicated IPA was alkaline.(Blue).

Two drops of .01 HCL brought it back to yellow.

Added 12 mL bio. Turned blue.

Titrated  0.230 mL  0.01 HCL to get back to yellow.

0.230 x 304 = 69.92 ppm.

That will do for me.

Title: Re: The Blues.
Post by: dgs on December 05, 2021, 11:03:43 PM
Good lad, I've always used about 17 drops of b ph b.
Title: Re: The Blues.
Post by: DavidA on February 23, 2022, 07:14:20 PM
I've used both and have both, there is very little difference. The soap test if done properly is about the quickest and most accurate of all the 'shed' tests. Make sure you blank off the ipa. With an accurate titration you can get a result of +/- 5ppm.

Just had an interesting( not to say frustrating) experience related to the above.

I was checking the soap content on my latest batch of bio. And couldn't get it to work at all.

It went ok until I added the oil. But immediately turned yellow instead of the blue I was expecting prior to adding the HCL to do the titration.

After three (yes, three) attempts it dawned on me that I was using Bromothymol Blue by mistake (It is in a similar bottle to the Bromophenol blue) .

The fourth attempt, using Bromophenol Blue worked out fine.

So, best avoid Bromothymol blue altogether.
Title: Re: The Blues.
Post by: knighty on February 24, 2022, 10:41:18 PM
After three (yes, three) attempts it dawned on me that I was using Bromothymol Blue by mistake (It is in a similar bottle to the Bromophenol blue) .
The fourth attempt, using Bromophenol Blue worked out fine.
So, best avoid Bromothymol blue altogether.

I'm dyslexic, I had to read that about 7 times to realise Bromothymol and Bromophenol are different things... I thought you'd made a mistake and repeated the same word each time :-o