Alternative Developing Agents: p-Aminophenol, Ascorbate, Glycin, Catechol, Pyrogallol
Metol and hydroquinone answer most of the questions a developer is asked, which is why they answered them for a century. The five agents on this page exist because of the questions they do not answer: how to sell a developer as a small bottle of syrup, how to build one with no quinol in it at all, how to make a bath whose development time you can compute from its dilution, and how to make an image that is partly not silver.
Each section here asks the same question — what does this agent do that metol and hydroquinone do not? — and refuses the alternative question, which is which one is best.
The five, and where their donor groups stand
- p-Aminophenol — hydroxyl and amino, para — the parent of metol and of every Rodinal-type concentrate
- Glycin — p-aminophenol with a carboxymethyl group on the nitrogen; not the amino acid glycine
- Catechol — two hydroxyls, ortho — hydroquinone’s isomer and nothing like it in behaviour
- Pyrogallol — three hydroxyls in a row; three ionisable groups and more ways to be oxidised
- Ascorbic acid — a lactone, not a benzene ring; it came from food chemistry, not from the dye works
p-Aminophenol: a solubility problem solved backwards
Section titled “p-Aminophenol: a solubility problem solved backwards”A Rodinal-type developer is a small bottle of dark syrup used at one part in twenty-five or one in fifty, and the reason it can exist in that form is a defect turned into a feature. Para-aminophenol barely dissolves in water — the published figures span more than sixteenfold, from under 1 mg/mL to 16 mg/mL, but every one of them puts it one to two orders of magnitude below hydroquinone’s 70 g/L. Put enough sodium hydroxide in with it and it dissolves in its own alkali, and what leaves the factory needs nothing but water.
Wall’s 1924 formulary prints the working of it, in an Ermen formula of the rodinal type: 50 g of the hydrochloride and 150 g of potassium metabisulfite in about 625 cm³ of water, with caustic soda added under constant stirring. “At first a precipitate of the paramidophenol base is formed, but, as more caustic soda is added, this dissolves.” Then the instruction that makes the formula: add enough soda to nearly dissolve the precipitate, and “it is very important to leave some undissolved”. The bottle is held deliberately at saturation, with solid base in equilibrium above the solution. Wall gives the instruction and not the reason, and no source this course holds supplies one.
The IUPAC dataset puts a number on the acid–base half of it: 4-aminophenol has a pKa of 10.46 at 25 °C for loss of the phenolic proton. A carbonate developer at pH 10 has a minority of the molecules ionised; a caustic concentrate is well past it. Kodak’s own primer ranks para-aminophenol, which it sold as Kodelon, between pyro and metol on its bromide-tolerance scale, and notes that Kodelon can be substituted for metol but that more of it is needed for a developer of the same strength.
Ascorbate: the developer with no quinol in it
Section titled “Ascorbate: the developer with no quinol in it”Kodak’s XTOL sheet leads with two claims about the same product: “ascorbic acid-based” and “no hydroquinone”. The first says what it contains, the second what it does not, and the fact that both are printed as benefits is the whole story of the last thirty years of developer chemistry.
Ascorbic acid is the one agent in this part that is not a substituted benzene ring. ChEBI describes a five-membered lactone carrying a two-carbon side chain, and CAMEO’s datasheet carries a reactivity alert reading simply Strong Reducing Agent. It reaches a developer already ionised: the IUPAC dataset gives pKa₁ 4.04 at 25 °C, so at any developer pH the molecule has long since given up its first proton and what is present is the ascorbate anion.
That has a formulation consequence which is the reason the salts exist.
A solution of the free acid is acid, and it will eat the carbonate or borate the developer needs before the developer can use it, in proportion to how much reducing agent you wanted. Sodium ascorbate does not, and CAMEO puts its aqueous pH at 5.6 to 7.0 or higher. Mole for mole the swap is a ratio of molar masses, 198.11 ÷ 176.12 = 1.125, and that factor answers the question about ascorbate ions and no part of the question about pH.
Where it works is the striking number. Kodak specifies XTOL’s working tank solution at pH 8.20 ± 0.05. Set that against ILFORD’s 10.30 to 10.50 for Bromophen stock and the ascorbate developer is running two orders of magnitude lower in hydrogen-ion concentration than the paper developer, and half a unit below ILFORD’s own ID-11. Kodak’s primer supplies one consequence immediately: alkalis soften the gelatin, so too alkaline a developer over-swells the coating and gives trouble with frilling. A bath at pH 8.2 asks less of the emulsion than one at 10.4.
And the isomer. Foma’s Fomatol P is described on its own sheet as a phenidone–isoascorbate developer. Erythorbic acid and its salts are a different stereoisomer of the same formula, with a different PubChem record and a different CAS number, and the photographic literature runs the two together constantly. The course names what the sheet names and treats them as distinct substances until it has a source that says otherwise. The practical point for a formulator is the one that always applies to isomers: the same formula is not the same substance, and the previous page made that argument with three molecules of C₆H₆O₂ of which one does not develop at all.
Glycin: the developer whose time you can calculate
Section titled “Glycin: the developer whose time you can calculate”Dilute a glycin developer to a tenth and it takes very close to ten times as long. That sentence is the whole of glycin’s reputation, and after the Wratten and Wainwright measurements above you can see why it is worth having.
Wall states the rough rule that a developer’s energy varies with its dilution, then the exception: Mees had shown a large departure from it with metol and hydroquinone, and also when air is dissolved in the water, but “with glycin and pyro-soda time seems proportionate to dilution”, and those two “seem to be the only developers that are not affected by the water”. A developer whose time you can compute, and which does not change its mind when the tap does, is a developer you can leave alone for an hour.
That is exactly how it was used. The 1906 British Journal Photographic Almanac prints Hübl’s directions for stand development: one ounce of the concentrated glycin stock in 80 to 90 ounces of water with 80 minims of ten per cent bromide, in which a properly exposed plate “should make its appearance in 15 or 20 minutes, and obtain full density in several hours”, with caustic soda added for under-exposure and more bromide for over-exposure.
Two more numbers characterise it. Wall’s tables of the Watkins factor — total development time divided by the time the image first appears — give glycin with sodium carbonate as 8 and with potassium carbonate as 12, against 30 for metol, 14 for metol–hydroquinone and 5 for hydroquinone with minimum bromide. A small factor means the image appears late in its own development, which is what an even-working agent does; and the fifty per cent jump from swapping one alkali for another is a reminder that an agent’s behaviour is never the agent’s alone. And on fog, the 1906 almanac reports Lüppo-Cramer’s comparison under a heavy bromide addition: pyro and adurol gave appreciably more fog than the hydroquinone standard, “edinol and glycin, less; pyrocatechin, none; metol, a trace” — the experimental version of Wall’s word clean.
Its structure explains none of that, and the course says so. Glycin is para-aminophenol carrying a carboxymethyl group on its nitrogen — not a dihydroxybenzene, and not the amino acid glycine. Why that added acid group should slow the agent down, and why it should fog so much less under bromide, is outside what this course’s sources establish, and the IUPAC dataset carries no dissociation constant for the molecule at all, so even the alkali dependence is read off the formulas rather than calculated.
Catechol and pyrogallol: when the oxidation product is the point
Section titled “Catechol and pyrogallol: when the oxidation product is the point”Every other agent in this part is judged partly by how little of its oxidation product ends up in the film. These two are judged by how much.
They are the ortho and the triol of the same family: catechol with two hydroxyls adjacent, pyrogallol with three in a row. The IUPAC dataset gives catechol pKa₁ 9.23 to 9.45 near room temperature and pyrogallol pKa₁ 9.05 to 9.28 at 20 °C, so both sit close to hydroquinone’s 9.88 and both need a real alkali; pyrogallol’s pKa₂ near 11.2 and pKa₃ near 14 are the bookkeeping behind Kodak’s observation that pyro oxidises far more readily than Elon or para-aminophenol for a given amount of preservative.
One dial: what sulfite does to a pyrogallol image
- No sulfite — a very yellow negative — image part silver, part oxidised pyrogallol
- Sulfite present — much less yellow: the sulfite is oxidised instead of the agent
- A great deal of sulfite — almost as blue an image as with Elon, whose product is not deposited coloured
Kodak’s account of the preservative is written around pyro precisely because pyro shows it best, and it is a graded experiment rather than an assertion: no sulfite gives a very yellow negative whose image consists partly of silver and partly of oxidised pyrogallol; sulfite gives a much less yellow one, because the sulfite is oxidised instead; a great deal of sulfite gives almost as blue an image as Elon, whose product is not deposited in a coloured form. Sulfite is the dial, and a staining developer is simply this dial turned down.
Bergger’s current datasheet for PMK describes the same effect as the product feature: a yellow-green tint surrounds each silver grain and fills the space between the grains, so that the density of a pyro negative is the conjunction of two densities, that of the silver and that of the coloration. Everything downstream on that sheet exists to protect the second density — a non-acid stop bath, a non-tanning fixer, a twenty to thirty minute wash because the colouring intensifies during washing, and no hypo eliminator, which weakens it.
Tanning is the other half of the same oxidation. Eder records Warnerke’s
report of 1881 that a gelatine film developed with pyro was soluble in warm water where it had not been
exposed and insoluble where it had. The course can name neither the yellow oxidation product nor the
mechanism by which it cross-links gelatin, and asserts neither; what is established is that the
product is coloured, that it deposits with the silver, and that the gelatin hardens where development
happened. staining-and-tanning-developers takes the practice, the published formulae and the hazard
assessment.
Comparative hazards, and the two that are not treated alike
Section titled “Comparative hazards, and the two that are not treated alike”The five differ far more in their hazard records than in their chemistry, and the differences are not where photographic folklore puts them.
| Agent | Signal word | The statements that decide the handling | Encyclopaedia level |
|---|---|---|---|
| Ascorbic acid | none | 97.3% of 588 reports say it meets no GHS criterion | A |
| Sodium ascorbate | none | 98.9% of 361 reports say it meets no GHS criterion | A |
| Glycin | Warning | H315, H319 at 100%, H335 at 97.7% — on only 44 reports | B |
| para-Aminophenol | Warning | H302, H341, H410 unanimous; H332 harmful if inhaled at 99.5%; H317 and H373 at 34.3% each | B |
| Pyrogallol | Warning | H312, H332 and H341 all at 100%; H302 and H412 above 93% | B |
| Catechol | Danger | H315 above 99.9%, H319 at 94.6%; H301 and H311 (toxic by mouth and skin) at 16.4%; H350, may cause cancer, at 11.4% | C |
Three readings follow, and each one contradicts something people say about these substances.
Pyrogallol is not the most heavily classified agent on the page — catechol is. Catechol carries
Danger, a minority classification as toxic rather than merely harmful by two routes, and a
carcinogenicity statement from 11.4 per cent of 2,962 reports, which PubChem reinforces with the
California Office of Environmental Health Hazard Assessment’s statement citing IARC. That is why the
encyclopaedia places catechol at Level C, where a fume cupboard or a licensed waste route is the
recognised control, and pyrogallol at Level B. Remember what a level means, though: the letter is a
hazard assessment of a procedure, so a page’s rating comes from what that page asks you to do, and
staining-and-tanning-developers makes its own assessment rather than inheriting these.
Pyrogallol’s danger is not the one the datasheets emphasise. Its three unanimous statements are harmful in contact with skin, harmful if inhaled, and suspected of causing genetic defects, while the two irritation statements are notified by only 12.3 per cent — the reverse of the usual pattern. Bergger’s own datasheet is blunter than the codes: pyrogallol is toxic by inhalation, skin contact and ingestion, causes kidney, liver and circulatory disorders, is a phenol and can cause burns, and brief skin contact may leave a dark stain while prolonged contact gives a burn resembling a heat burn. There is no NIOSH entry and no EH40 exposure limit, so there is no airborne figure to work to.
The mildest record on the page belongs to the newest agent, and thinness is not the reason. Ascorbic acid’s 588 reports and sodium ascorbate’s 361 are respectable numbers, and 97 to 99 per cent of them report no GHS criterion met. That is a real finding rather than an absence of one — unlike glycin, whose 44 reports across four notifications are among the smallest evidence bases in the encyclopaedia, and for which the course could locate no CAMEO datasheet, no safety card, no NIOSH entry and no exposure limit. Glycin’s mild classification and ascorbate’s mild classification are not the same kind of statement, and reading them as if they were is the most common mistake made with hazard data.
- Every one of these agents exists because of something metol and hydroquinone cannot do, and the four benzene-ring agents all satisfy the same para-or-ortho rule as the classical pair. Ascorbic acid satisfies none of it.
- Para-aminophenol dissolves in its own alkali, which is why a Rodinal-type developer can be a bottle of syrup used at 1+50 and why Foma’s para-aminophenol concentrate develops 25 films per package against 12 for its phenidone–hydroquinone one. Its pKa is 10.46; its temperature coefficient is 2.4; and at high dilution the time is not proportional to the dilution, as Wratten and Wainwright showed with 42, 46 and 52 minutes for three different waters where arithmetic predicted 30.
- Ascorbate arrives already ionised — pKa₁ 4.04 — which is why the acid form eats the alkali and why the salt exists, at a substitution factor of 1.125 by mass. XTOL runs at pH 8.20, two orders of magnitude below a paper developer.
- On ascorbate keeping the course has two Tier-1 sources that disagree: CAMEO’s rapid air oxidation above pH 6, accelerated by iron and copper and continuing anaerobically, against Kodak’s advertised resistance to oxidation and six-month shelf life. The community’s sudden-failure reports are Tier-3 and are excluded rather than used as a tie-breaker.
- Glycin’s development time is proportional to its dilution and indifferent to the water, which is the property that made it the stand developer of its period. Its Watkins factor is 8 with sodium carbonate and 12 with potassium, and Lüppo-Cramer found it among the cleanest agents under heavy bromide. Why, is not something this course can source.
- For catechol and pyrogallol the oxidation product is the image. Sulfite is the single dial between a stain image and a plain silver one, and the tanning of the gelatin is recorded from 1881 without the course being able to name the chemistry that does it.
- Catechol, not pyrogallol, is the most heavily classified agent here — Danger, a minority toxic classification, a carcinogenicity statement, and Level C in this encyclopaedia. And a mild classification means one thing for ascorbate, with 588 reports behind it, and something quite different for glycin, with 44.
Check your understanding
Sources for this page
17 cited · checked 2026-09-04
- 01Elementary Photographic ChemistryEastman Kodak Company, 1928§ Chapter III: para-aminophenol and its methylated derivative, Kodelon as the oxalate, the reduction-potential ranking, the graded sulfite experiment with pyrogallol and the colour of the resulting negative; Chapter VII: two-solution storage for readily oxidisable agentsarchive.org/details/elementaryphotog00east_0tier 1, primary2026-09-04
- 02Photographic Facts and FormulasE. J. Wall, F.C.S., F.R.P.S., 1924§ Developers — the rodinal-type liquid developers and Ermen's formula with its instruction to leave some of the base undissolved; Pyrocatechin formulae; Stand development and the Wratten & Wainwright dilution measurements; Glycin, glycin-soda and glycin-potash factorsarchive.org/details/photographicfact00walltier 1, primary2026-09-04
- 03The Dictionary of Photography and Reference Book for Amateur and Professional Photographers, 9th editionE. J. Wall, edited by F. J. Mortimer, 1912§ Glycin; Development and Developers — Watkins factors, temperature coefficients, dilution and time, stand or tank developers; Pyrocatechinarchive.org/details/dictionaryofphot1912walltier 1, primary2026-09-04
- 04The British Journal Photographic Almanac and Photographer's Daily CompanionEdited for the British Journal of Photography, 1906§ Stand development with Hübl's concentrated glycin solution; Developers for Reproduction (Sturenberg), page 789; Dichroic Fog and Developers (Lüppo-Cramer), page 789archive.org/stream/britishjournalph1909unse/britishjournalph1909unse_djvu.txttier 1, primary2026-09-04
- 05History of PhotographyJosef Maria Eder, translated by Edward Epstean, 1945§ Organic developer substances — Eder and Toth 1880 on isomerism in the bivalent phenols and the later extension of the rule to paramidophenol; Andresen's German patent 60174 of 27 January 1891 for paramidophenol, rodinal; Warnerke 1881 on the tanning of gelatine by pyro developmentarchive.org/details/EderHistoryPhotographytier 1, primary2026-09-04
- 06KODAK PROFESSIONAL XTOL Developer, Technical Data / Chemical, J-109Kodak Alaris Inc., 2018§ Features and benefits: ascorbic acid-based, no hydroquinone, excellent keeping properties and high resistance to breakdown from oxidation; mixing at 18 to 30 degrees C; the working tank solution at pH 8.20; storage life six months full and at least two months partially filledbusiness.kodakmoments.com/sites/default/files/wysiwyg/pro/chemistry/J-109_Feb_2018.pdftier 1, primary2026-09-04
- 07Developers for black-and-white negative films (Fomadon)FOMA BOHEMIA spol. s r.o., 2023§ FOMADON R09, a liquid concentrate of a fine-grain normal-working para-aminophenol negative developer at 1+25 or 1+50 with a stated capacity of 25 films per package; FOMADON LQN and its capacity of 12 films per packagefoma.cz/en/filmtier 1, primary2026-09-04
- 08Developers for black-and-white photographic papers (Fomatol)FOMA BOHEMIA spol. s r.o., 2023§ FOMATOL P, a two-component phenidone-isoascorbate normal-working positive developer in powder formfoma.cz/en/papertier 1, primary2026-09-04
- 09BERGGER PMK DatasheetBERGGER, 2020§ PMK properties: the yellow-green tint surrounding each silver grain and the density of a pyro negative as the conjunction of two densities; capacity and temperature range; toxicitybergger.com/fr/index.phptier 1, primary2026-09-04
- 10IUPAC Digitized pKa Dataset, high-confidence subset v2.3International Union of Pure and Applied Chemistry, Dissociation Constants project; digitised from the Serjeant and Dempsey and Perrin compilations, 2024§ Entry perrin: 4-aminophenol pKa; entry serjeant2830 and neighbours: 1,2-benzenediol pKa1 and pKa2; entry serjeant2832: 1,2,3-benzenetriol pKa1, pKa2 and pKa3; L-ascorbic acid pKa1 and pKa2github.com/IUPAC/Dissociation-Constantstier 1, primary2026-09-04
- 11CAMEO Chemicals: chemical datasheets and reactivityNational Oceanic and Atmospheric Administration, Office of Response and Restoration§ ASCORBIC ACID datasheet — reactivity alert Strong Reducing Agent, air and water reactions including the acceleration of oxidation by alkaline conditions, iron and copper and the degradation under anaerobic conditions; SODIUM ASCORBATE — quick air oxidation above pH 6; CATECHOL and PYROGALLIC ACID datasheetscameochemicals.noaa.govtier 1, primary2026-09-04
- 12PubChem compound summary: Catechol (CID 289)National Center for Biotechnology Information§ GHS classification — the aggregated ECHA notifications and the proportions behind each statement; the California OEHHA statement citing IARCpubchem.ncbi.nlm.nih.gov/compound/289tier 1, primary2026-09-04
- 13PubChem compound summary: Pyrogallol (CID 1057)National Center for Biotechnology Information§ GHS classification — the aggregated ECHA notifications and the proportions behind each statementpubchem.ncbi.nlm.nih.gov/compound/1057tier 1, primary2026-09-04
- 14PubChem compound summary: N-(4-Hydroxyphenyl)glycine (CID 67149)National Center for Biotechnology Information§ GHS classification — the aggregated ECHA notifications; ChEBI description and its allergen rolepubchem.ncbi.nlm.nih.gov/compound/67149tier 1, primary2026-09-04
- 15PubChem compound summary: 4-Aminophenol (CID 403)National Center for Biotechnology Information§ GHS classification — the harmonised CLP entry and the aggregated ECHA notifications; solubilitypubchem.ncbi.nlm.nih.gov/compound/403tier 1, primary2026-09-04
- 16PubChem compound summary: L-Ascorbic Acid (CID 54670067)National Center for Biotechnology Information§ GHS classification — the aggregated ECHA notifications, of which 97.3 per cent report that the substance does not meet GHS criteriapubchem.ncbi.nlm.nih.gov/compound/54670067tier 1, primary2026-09-04
- 17Chemicals and Formulae, 3rd edition (one of a series of Kodak photographic handbooks)Kodak Limited, 1949§ Some Kodak tested chemicals, including Calgon (sodium hexametaphosphate) among the substances sold for darkroom usearchive.org/details/KodakChemicalsAndFormulaetier 1, primary2026-09-04
Formulas, hazard statements, historical dates and process descriptions on this page were checked against the sources above on the date shown. Safety data changes: obtain the current safety data sheet for the product you actually buy before you open it.