RE: Lithium palladium vs. "normal" palladium
Hi Eric, "molar solution" Well, since I had my chemistry classes in Turkish, I may not use the correct English terms. Please read my message again by reply "x in y" expression with "x + water to make y" (because this is what I do when I mix my solutions) and tell me if there's any mistake and/or am I right in my confusion. Will look at the archives BTW... "knowledgeable person" My calculations and the results of them matches the calculations/results of a person you'll admit is very knowledgeable; see how M. Ware mixes his metal solution in his article http://www.mikeware.co.uk/mikeware/Platino-Palladiotype.html: "The palladium solution (Pd) ... To make up: 1. Dissolve 1.8 g Ammonium Chloride in about 20 cc of hot (70-80 °C) distilled water. 2. Add 3 g Palladium(II) Chloride with stirring (which should be well-powdered. HAZARD: wear a dust mask) ..." If you put 3g in place of 25g for PdCl2 in my calculations below, you'll find that indeed you need 1.8g (NH4)Cl to make the (NH4)Pd double salt solution by using 3g PdCl2. Probably there's something with Li which necessitates using 50% in excess -> but this is surely confusing when you look the process equations (because they don't tell us we'll need excess salt!?). "misread" I don't misread Jeffrey, I just compare the figures I found (my making the calculations below) with the figures given by his "Metal Solution Formula Calculator" using the same sensitizer strength, Pd double salt and target volume... See for yourself. "rich print" Well, I guess someone (including myself) has to mix the solutions according to the calculations below and share their finding with the list later. (I mean to report if their prints are as rich as they were before...) Regards, Loris. -----Original Message----- From: EJN Photo [mailto:ejnphoto@sbcglobal.net] Sent: 18 Ocak 2007 Perşembe 05:35 To: alt-photo-process-l@usask.ca Subject: RE: Lithium palladium vs. "normal" palladium Loris, First a molar solution is not "in" but "to make". It would be a normal solution not a molar solution. Your confusion about the information in TNPP book, was documented in the archives. Why B&S/Sullivan stayed with that number I don't recall. And any time someone starts writing down numbers and formula, it is always a good idea to have another knowledgeable person read it, and read it again because it is so easy to misplace a letter or period and make a formula mistake. I also think that you are adding to the confusion by bringing ingredients into the discussion in forms that are not being used. We don't, at least I don't, typically mix our double salts from solutions mixed to molar concentrations but by adding solids to water. i.e. X grams of A chloride with Y grams of Palladium Chloride with water to make Z ml of solution. It is at this point that we have our solution hopefully made to our targeted molar concentration. AS to confusion #1, If Jeffrey wrote it down that way, it is wrong. I don't recall his numbers being that far off in any correspondence that I had with him several years back when he was working through those numbers. It could also be that you misread Jeffrey? The idea behind his work was to get a solution that wasted as little expensive metal salt as possible and to produce the richest print as well. Where richest is not money, but tonally rich. Skype : ejprinter> -----Original Message----- > From: Loris Medici [mailto:mail@loris.medici.name] > Sent: Wednesday, January 17, 2007 2:22 PM > To: alt-photo-process-l@usask.ca > Subject: RE: Lithium palladium vs. "normal" palladium > > Hi Witho, > > Thanks for bringing this up. I did some calculations and I'm quite > confused right now. See below: > > LiCl (Lithium Cloride) 1 Mole = 42.394g, > 1.4M solution = 59.3516g in 1000ml (5.93%) > > (NH4)Cl (Ammonium Chloride) 1 Mole = 53.4912g, > 1.4M solution = 74.88768g in 1000ml (7.48%) > > PdCl2 (Palladium(II) Chloride) 1 Mole = 177.33g, > 0.7M solution = 124.131g in 1000ml (12.41%) > > Li2[PdCl4] (Lithium double salt of Pd) 1 Mole = 262.11g, > 0.7M solution = 183.477g in 1000ml (18.34%) > > (NH4)[PdCl4] (Ammonium double salt of Pd) 1 Mole = 284.31g, > 0.7M solution = 199.017g in 1000ml (19.9%) > > (NH4)3[Fe(C2O4)3].3H2O (AFO) 1 Mole = 428.067g, > 1.4M solution = 599.2938g in 1000ml (59.92% - say 60%) > > 2 Mole salt + 1 Mole PdCl2 -> 1 Mole Pd double salt. Therefore > > 2 LiCl + 1 PdCl2 -> 1 Li2[PdCl4] > 2 (NH4)Cl + 1 PdCl2 -> 1 (NH4)2[PdCl4] > > If you compare the atom counts on each side you'll see that the > equations are correct. > > To Camden: > > Let's assume you have 25g PdCl2 (current special price for this amnt. > for APUG.org members is $262.50 (+ 135g Ferric Oxalate for free > - > kudos B&S). .. > > You can make 200ml (201.45 actually) 0.7M Li2[PdCl4] solution with > this amnt. of PdCl2 (25g / 12.41% - see info provided for > PdCl2 above.) > > You'll need > > 25 (1) / 177.33 (2) * 2 (3) * 42.394 (4) = 11.95g LiCl. > > or > > 25 (1) / 177.33 (2) * 2 (3) * 53.4912 (5) = 15.08g (NH4)Cl > > Notes: > (1) Amnt. of PdCl2 you have > (2) Molar Mass of PdCl2 > (3) 2:1 salt to PdCl2 ratio > (4) Molar Mass of LiCl > (5) Molar Mass of (NH4)Cl > > Calculate your costs according to the info I gave you above. > > To Witho and all: > > Lets assume you want to use 60% AFO as iron sensitizer, this is 1.4M > solution. If the molar ratio of AFO to Pd double salt is 2:1, > then the > Pd double salt solution should be 1.4 / 2 = 0.7M. This is > totally > consistent with the formulas given in Mike Ware's "The > Platino-Palladiotype Process" article... (Sensitizer's > concentration > is 1.4M whereas the Pd double salt concentration is 0.7M.) When > I > crosscheck this using Jeffrey's metal solution calculator, I > can see > that he uses 1.4M Pd double salt for 1.4M AFO sensitizer - in > other > words 2x of what is really needed. Isn't this wasting precious > metal? > (I always had the feeling that I was loosing Pd when doing > Ziatypes, > because the clearing bath was a light shade Pd brown - instead > of the > yellow I get in other iron processes...) This is confusion > #1... > > Also, when I check the amount of salt and PdCl2 for making up the Pd > double salt solution (from the book "The New Platinum Print" by > Sullivan and Weese, see page 76), the amounts I find are not > consistent with the amounts stated. > > The book says 1.7g LiCl + 2.3g PdCl2 + water to make 25ml, if we > interpolate this as we're using 25g PdCl2 -> > > 25 / 2.3 ~= 10.87, 10.87 x 1.7 ~= 18.47 <- the amnt. of LiCl needed > according to the book. Instead, the formula tells us we > actually need > 11.95g of LiCl2 - in other words, ~1.5x times. This is > confusion #2... > > I'd like to hear your comments confusions #1 and #2. What am I > missing? > > Thanks in advance (and for taking the trouble of reading all this up > to here), Best regards, > Loris. > > -------------- Quotation below -------------- > > Hello Eric, > > It is good that you mention this. > > I did some reading again last week on the available chemistry > publications and there is something my eye fell on. Mike Ware states > that the molar ratio > of ammonia ferric oxalate to ammonia tetra chloro palladate is > 2 :1 to > complete the reaction: > > Reaction 1 > > hv = 2[Fe(C2O4)3]3 => 2[Fe(C2O4)2]2- + C2O42- + 2CO2 > > Reaction 2 > > [PdCl4]2- + 2[Fe(C2O4)2]2 => Pd + 2[Fe(C2O4)2]- + 4Cl- > > But, if you read the manual of Jeffrey Matthias (which I took for a > long time as my guide) you will see that he uses a ratio of 1:1 > > (NH4)3Fe(C2O4)3.3H2O >exposure> Fe(C2O4)2 + 3(NH4) + 3H2O + 2CO2 > > 3Fe(C2O4)2 + 3Li2PdCl4 + 3(NH4) + 3H2O => (NH4)3Fe(C2O4)3.3H2O + > 2(FeCl3) + 6LiCl + 3Pd + 3(C2O4) > > And Jeffrey states also : 'Or other metallic salts could be > substituted. Every three sensitizer molecules will pair with three > metallic double salt > molecules, a one-to-one ratio (1 metal salt for 1 sensitizer).' > > This difference is substantial. I asked Mike Ware about it and Jeffrey > Matthias. Jeffrey replied me as follows : > > 'Remember that my work is based on empirical study, not theoretical. > This means that I am explaining things as they show themselves to > behave through > experimentation, not by the science of what they should or are > doing. I > realized that I do not have the training and experience in > ionic theory as > others, but I did have the time and patience to carefully run > some > calibrated experiments. > > If the suggestion is that a print can be made with less metal than the > threshold, the result will be a weak print. Additional metal > will just be > wasted. The statement: > "The correct stoicheiometry for trisoxalatoferrate(III) to > chloropalladate(II) in the sensitizer is indeed 2:1."(quoting > Mike Ware in > an e mail to me) " is hard for me to understand. This is why I > like to use > the compound's formulae rather than its name. I suspect that > what is being > called 2:1 is the same as I have called 1:1. The bottom line is > figuring how > much of each substance to put into the solutions. What I call > 1:1 is > consistent with historic formulas and works. If this is really > 2:1 then so > be it. But, if it is suggested that twice or half as much > sensitizer is to > be used or twice or half as much metal solution, I know that > will produce a > problem in the print.' > > Of course my suggestion to Jeffrey was not 'that a print can be made > with less metal than the threshold' but that you loose a lot of > metal if the > ratio of the reacting compounds is not right. My suggestion is > to run a > series of new tests with the different (2:1) ratio's. > > I have not calculated the B&S concentrations so I can't say from what > equations they start. Maybe Richard can tell us some more about > it? > > Witho > > -----Oorspronkelijk bericht----- > Van: Eric Neilsen [mailto:ejnphoto@sbcglobal.net] > Verzonden: woensdag 17 januari 2007 0:52 > Aan: alt-photo-process-l@usask.ca > Onderwerp: RE: Lithium palladium vs. "normal" palladium > > > Eric, > > > > Thanks for the information; it's amazing how much there is to > learn about > > pt/pd printing. > > > > > > > 2 Moles of [Li, NH4, Na] Cl, to 1 mole of > > > PdCl2. How you decide to dilute it is up to you. > > > > How do different dilutions affect the print (color, dmax, > etc.)? Just out > > of curiosity, which dilutions do you (and others) use? > > > > The idea is to match the solution strength of the metal salts with > that of the Ferric; either AFO or FO. One can get bad Dmax or extra > contrast > depending on which way the equation is set. > > > > > > How does one make there AFO, or FO is equally > > > important. The numbers are not etched in stone but the > results nearly > > are > > > :) > > > > Not sure I'm following you here. Are you saying that there > is an "ideal" > > dilution of AFO/FO for a given dilution of pd, or are you > simply saying > > that the AFO/FO dilution, whatever it may be, plays a > significant role in > > print results? > > > > Yes, equal to required needs. When you look at % solutions and > matching them with molar solutions, that can be an easily lost battle > unless you know the > equivalent for each. What is a molar solution? A 1 molar > solution is the > formula weight to make 1 liter of solution. Note I did not say > add to 1 > liter different solution. You can see in Ware/Malde there is a > .7M solution > of both the ammonium based palladium and platinum salts. The > AFO is mixed at > 1.4M. And I see the mixing of solution / reactants like this, > > If you are going to error on one side or the other you should error on > the side of too much of the catalyst. So for mixing your metal > salts, the extra > would come in the form of a little extra chloride cation _ the > sodium, > ammonium, lithium, because with out it, the PdCl2 can not get > into solution. > And like wise, add extra AFO,FO because without it the precious > solution of > PT / PD will sit in the paper with no enough available Ferric > to convert it > into the new "black" state that forms your print. > > I mix my solutions as close to .7 M as possible. The B&S solution are > quite a bit less than .7 M. That is not to say that they are wrong, > but it might > be a possible reason that many seem to require and extra > coating to get good > Dmax. Jeffrey Mathis has an extensive write up about > optimizing the > solutions. I might not agree with everything there, the idea is > a good one. > Coat a variety of amounts, and see what gives you the best > Dmax, color, > contrast. Find out what this ingredients really do, not just > what someone > else has settled on. > > Eric Neilsen Photography > 4101 Commerce Street > Suite 9 > Dallas, TX 75226 > http://e.neilsen.home.att.net http://ericneilsenphotography.com > Skype ejprinter
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