Using TF4, testing for residual fixer?

Ok, so I think I messed up by spending ten bucks on Formulary's Residual Hypo Test. First, while this isn't mentioned on their product page, the instructions indicate that it can't test for archival washing. Second, they mention that it's no good for people that use Hypo eliminator because of the ammonia. Well, TF4 smells like ammonia to me.

Is the Formulary Residual Hypo Test suitible for use with TF4 fixed prints?

Can it really not tell me if my prints are truly, adequately washed?

What should I be using to test my prints for archival washing?

I use the Formulary residual hypo test and retained silver test with all fixers.

It seems to work ok for me.

PE

The same as PE for me, but I only use TF-4. I never heard anything about these not working with TF-4 anywhere, but I'm no expert so...

- Randy

I have the old Kodak archival test strip that you use to compare with the color of the paper. This tells you that you are safe or not.

It works with the Formulary product if you wash well enough.

The problem is that some wash aids can cause problems. Mason and Mees and James and others warn that you have to wash well after wash aids. It presents an interesting conundrum, doesn't it?

PE

Thanks all. I found some formulary documentation for TF4 and they recommend their residual hypo test (without mentioning the not-for-archival aspect they include in RHT instructions). I need to go find out about the retained silver test.

Speaking of which, I wanted to know if "exposure to light" in the context of the HT-2 test meant exposure to any light, incl. tungsten, or specifically to daylight?

There are a couple of different kinds of hypo test solution. None of them are sensitive enough to detect the levels of residual hypo that are usually specified for archival processing, but sequential use at different stages of the wash can certainly give you an indication of how effective your washing is. Then you can wash a bit longer (I don't know how much, but i would guess that 50 percent would do) and be sure of well washed prints.

The Formulary kit sounds like it is similar to Kodak HT-2, which is a silver nitrate solution. If you had excess ammonia or ammonium compounds on the print, they could reduce the sensitivity of the test. By the time you have rinsed the print, treated it with HCA (not the peroxide and ammonia brew called hypo eliminator - Kodak HE-1), and washed it a while, there will probably not be enough ammonium left to make much of a difference. Ammonium compounds are usually very soluble. Kodak tells us to keep HT-2 in a dark bottle and to use it in subdued light. Since it is a solution of silver nitrate and other things, you should handle it as at least somewhat light sensitive. If you don't, the solution will go bad and silver will precipitate of plate out.

jstraw said:

Thanks all. I found some formulary documentation
for TF4 and they recommend their residual hypo test
(without mentioning the not-for-archival aspect they
include in RHT instructions). I need to go find out
about the retained silver test.

Click to expand...

Some PF instructions must go back to Grandfather's day.
As mentioned, not HE-1, OK with hca.

Four + years ago I bought the HT-2 kit and 99% of it
is stored in small amber glass Boston Rounds. Within the
next week or two I'll test it against fresh. I read that it
does have a limited life span.

So, from PF I bought some silver nitrate. At the grocery
I bought a small bottle of White Vinegar. With vinegar,
Kodak, or without, Ilford, I've fresh HT-2 at test time.

I'll have to rethink the formula but it goes something like
this, 2 drops of AgNO3 + 2 drops H2O + 4 drops vinegar.
With vinegar, spots on paper even those which do not
show at test time, brown less over time. I blot with
tissue and do not rinse though I may add a rinse
in the future.

The HT-2 does not read AT archival levels but does
come close. IIRC, Ryuji has a some exact figure and
recommends the test. I'm satisfied with NO stain.

Check any Ilford FB PDF for info on the ST-1 test.
A very little amount of sodium sulfide is needed. Add
some potassium ferricyanide and bromide for sepia
toner. HT-2 or ST-1 a very little chemistry will
go a long long way. Dan

Is PF's Residual Silver Test: http://www.bhphotovideo.com/bnh/controller/home?O=productlist&A=details&Q=&sku=123416&is=REG
different than Kodak's ST-1 (which I can't seem to find.)

IDK if ST-1 is the same as the formulary test.

The Formulary test is basically Sodium Sulfide which turns black when it touches any silver ion. The density depends on the amount of silver present.

The residual hypo test is basically silver nitrate in acid that turns yellow when it contacts hypo and Kodak makes a color chart for matching this color against level in PPM.

PE

jstraw said:

Is PF's Residual Silver Test:
http://www.bhphotovideo.com/bnh/controller/home?O=productlist&A=details&Q=&sku=123416&is=REG
different than Kodak's ST-1 (which I can't seem to find.)

Click to expand...

Explore at www.unblinkingeye.com for archival processing.
The tests mentioned so far are described. Do I detect the
lack of a small capacity scale? Dan

dancqu said:

Do I detect the
lack of a small capacity scale? Dan

Click to expand...

For what purpose?

jstraw said:

For what purpose?

Click to expand...

Unless there is a need for large quantities of prepared
chemistry, fresh chemistry in small quantity can easily
be Home Brew. For example I weighed out 1.05 grams
of silver nitrate to use as the HT-2 test.

Photographers' Formulary is, IMO, out in front as
a source for chemicals. Why? Because they sell in
both small and not so small quantities. I consider the
Formulary an Essential supplier. They are the Only
supplier in the world of glycin. A comparison with
other suppliers will likely reveal other chemistry
which they only supply.

Of course competition keeps them honest and fills
in here and there where the Formulary lacks. Dan

Retained hypo test

There have been many questions about the hypo test solution sold by Kodak and the Formulary. It is used by many including myself and I find that it works fine.

Here is a scan of the Kodak test kit and formula for Kodak's test. I am using this excerpt to illustrate the test method and to alert people to the test chart and instructional information.

This does not violate copyright for a number of reasons. Among them are:

1. The formula is in the public domain.
2. The original test chart is color, and mine is B&W
3. The instructions are two sides of detailed information which my scan does not show.

The final note is that the Formulary product appears to be identical to the Kodak product.

PE

Perhaps I should have spelled it GlycinE. ".. hasn't been used in
the industry for a few decades," That may be true. There are
though more than a few Apugers who swear by it. It's on
my buy list for a next PF order. Dan

Dan;

Glycin is correct. Glycine is an amino acid which will not develop anything photographically.

PE

OK, now I call bull pucky. I happen to be enjoying PF 130 of which glycin is an active ingredient. True, Ansco 130 has been out of production for many years because of Ansco's corporate demise. Just what characteristic warrants calling glycin obsolete?

Photo Engineer said:

There have been many questions about the hypo test solution sold by Kodak and the Formulary.

Click to expand...

Based on the formula available in Kodak publications and the spec sheet of the Formulary, the product they sell is identical to the HT-2 test. I hasten to add that the color charts are available in the "Darkroom Dataguide", also known as "Master Dataguide" in older incarnations. These guides sell for cheap cheap on the auction site (5$).

Michel;

Please refer to my post of the Kodak HT-2 test elsewhere. I show the formula and the Kodak test strip.

This is the problem with so many threads going on the same subject at the same time.

PE

mhv said:

Based on the formula available in Kodak publications and the spec sheet of the Formulary, the product they sell is identical to the HT-2 test. I hasten to add that the color charts are available in the "Darkroom Dataguide", also known as "Master Dataguide" in older incarnations. These guides sell for cheap cheap on the auction site (5$).

Click to expand...

If you have a densitometer, you can use the densitometer to read the numerical value of the residual thiosulfate level. The method was developed by Pope of National Bureau of Standard in 1969. If anyone is interested, I'll upload it to my website, as his papers are in public domain. Well, WTF. This paper is really short with no figures. So here it goes.

Again, this paper is in public domain, as it is written by a US Government worker on duty.

The text is uncorrected OCR. Beware of inaccurate conversions.


PHOTOGRAPHIC SCIENCE AND ENGINEERI~O
Volume 13, Number S, September-October 1969
A Simplified Method for Determining Residual-::¿".
Thiosulfate in Processed Microfllm*

C. I. POPE, Image Optics and Photography Section, Xational Bureau of Standards,
Washington, D.C. 20234

In the silver nitrate test for residual thiosulfate in processed film the silver ion reacts quantitatively
with thiosulfate to form silver sulfide in situ. The excess silver ion is removed by treating the
sample in solutions of sodium chloride and sodium thiosulfate followed by washing. The method
is simplified by using a solution of ammonium hydroxide and sodium chloride to remove the ex-
cess silver ion; no washing is necessary. The new method takes half the time previously required.

Residual thiosulfate in processed photographic
papers is usually determined by treating the paper
with silver nitrate, which reacts with the reactive
sulfur in thiosulfate to form silver sulfide in situ. L~
The silver nitrate also reacts with the reactive sulfur
in any trithionate or tetrathionate present to form
silver sulfide. Mattey and Henna adapted the
silver nitrate test to determine the residual thio-
sulfate in processed film. They removed the excess
silver ion by treating the sample in a sodium chlo-
ride solution, then a sodium thiosulfate solution,
and then washing. Any excess silver ion left in the
film would darken and increase the density of the
film. The purpose of this study was to simplify
the processing of the sample after treatment in the
silver nitrate solution. It was found that a 1 %
ammonium hydroxide solution containing 5 g of
NaCl per liter adequately removes the silver ion, .
and no washing is required. This treatment should
be effective on all types of silver films, but its
effectiveness on papers is unknown.

Experimental

Processed microfilm test samples were prepared
by treating 20-cm strips of unexposed film 1 min
in a developer solution, fixing them for 4 min in a
thiosulfate fixing solution, washing ~ to 11'2 min
in chlorine-free tap water, removing the surface
water immediately with wiping tissue, and drying.

The film strips were treated 4 min in a !"oilition
containing 10 g of silver nitrate and 30 ml of glacial
acetic acis per liter. In some test strips the exce:5S
silver ion was removed by treating them for 4 min
in a solution containing 45 g of sodium chloride
per liter, then for 4 min in a solution cont.aining 15
g of sodium sulfite and 45 g of sodium thiosulfate
per liter, and washing according to the recommen·
dations of Mattey and Henn.' Control !"amples
not treated in the silver nitrate solution were placed
in the sodium chloride solution. In other test
strips the excess silver ion was removed by treating
them for 2 min in a 1 % solution of ammonium
hydroxide containing 5 g of sodium chloride per liter,
removing the surface solution with wiping tissue
and drying. Control samples not treated in the
silver nitrate solution were placed in the ammonium
hydroxide-sodium chloride solution. The trans-
mission densities of the precipitated silver sulfide
in the gelatin layer was read on a commercial
densitometer equipped with a Kodak Wratten )Jo.
18A filter.
Several tests were made by the two procedures
for concentrations of residual sodium thiosulfate
ranging from 0.1 to 15 μg cm~ in processed micro-
film. The transmission densities were generally
slightly higher for the ammonium hydroxide-
sodium chloride fixation. For example, the trans-
mission densities of the silver sulfide in t.hree test
samples of single layer film were 0.05, 0.13, and
0.21 after treatment in the ammonium hydroxide-
sodium chloride solution but were, respectively,
0.04, 0.12, and 0.20 after treatment in the sodium
chloride solution and the sodium sulfite·sodium
thiosulfate solution. The cause of this difference
is not known. Prolonged treatment of the samples
in the sodium chloride solution or in the wdium
sulfite-sodium thiosulfate did not decrease the
transmission density of the silver sulfide, indicating
no removal of the silver sulfide hy these solutions.
However, calibration curves may be prepared for
either procedure by plotting the residual sodium
thiosulfate content against the density of silver
sulfide in processed microfilm of known sodium
thiosulfate content.
Test samples treated in the ammonium hydrox-
ide-sodium chloride solution did not show a measur-
able increase in transmission density when aged 16
hr at 50°C or treated 4 min in a developer solution,
washed and dried. These tests indicated that the
residual silver ion had heen adequately remowd.

Discussion

The simplified procedure for the residual thio-
:;ulfate test in processed microfilm uses two solutions
instead of three and washing of the test sample is
eliminated. The procedure should be applicable
to other types of film. Thicker films may necessi-
tate increasing the ammonium hydroxide concen-
tration or the time of fixation in the ammonium
hydroxide-sodium chloride solution. A calibration
curve may he made by the procedure given by
Mattey anrl Henna by either the methylene blue
test~ or the modified Crabtree-Ross test.';



Received March 24. 1969; rtlvi>led May 20, 1969.
• Contribution of Lh" Nationat Bureau of Standard •. not .\lhj.-.:I t.,)
copyright.
l. J. I. Crabtree, G. T. Eaton, and L. E. Muehl"r. A review of hyp.,
testing methods . .J. Soc. Malian Piclure Eng,.,.. 42: 34-57(1944).
2. American Standard Method for DetermininI': Hesidual Thiosulf~te
and Thionates in Proc.-essed Photographic Papers. PH4.30·1!>6~
(United States of America Standarda lnatitute. 10 East 40th St,..,.,!.
New York. N. Y. 10016).
3. D. A. Mattey and H. W. Henn, Determination of thio.'lUlf.te and
tbionates in film with .ilver nitrate, Photogr. &i. Eng. lO, 1'\0.4,
202-208 (1966).
4, C. D. Warburton and E. P. Przyhylowi~z, A new test method for the
measurement of residual thiosulfat.c in proc ...."Cd film based on boro-
hydride reduction to sulfide and m"thylpnp blue formation, Photogr.
S~i. Eng. 10: 86-92(1966).
"~o C. I. Pope, Det.crmination of residual thiosulfate in processed film.
J. /t ... NBS 67C (Engr. and Instr.), 3: 23; ¡ 1!l63}.

mhv said:

Based on the formula available in Kodak publications and the spec sheet of the Formulary, the product they sell is identical to the HT-2 test. I hasten to add that the color charts are available in the "Darkroom Dataguide", also known as "Master Dataguide" in older incarnations. These guides sell for cheap cheap on the auction site (5$).

Click to expand...

Moments ago I bought a used copy from an Amazon seller with good feedback. 1996 edition, "like new" condition for $4.00 plus shipping.

Photo Engineer said:

Michel;

Please refer to my post of the Kodak HT-2 test elsewhere. I show the formula and the Kodak test strip.

This is the problem with so many threads going on the same subject at the same time.

PE

Click to expand...

Oh, I saw the scan, I just meant to underline that the color version is available for cheap at auction.

jstraw said:

Moments ago I bought a used copy from an Amazon seller with good feedback. 1996 edition, "like new" condition for $4.00 plus shipping.

Click to expand...

It should also have the formulae for HT-2 and ST-1. Based on my 1970-ish edition, the Formulary's kits are identical.

Ryuji said:

If you have a densitometer, you can use the densitometer
to read the numerical value of the residual thiosulfate level.
The method was developed by Pope of National Bureau of
Standard in 1969.

Again, this paper is in public domain, as it is written by a
US Government worker on duty.The text is uncorrected
OCR. Beware of inaccurate conversions.

PHOTOGRAPHIC SCIENCE AND ENGINEERI~O Volume 13,
Number S, September-October 1969 A Simplified Method
for Determining Residual-::¿". Thiosulfate in
Processed Microfllm*

Click to expand...

Very interesting. I do use the silver nitrate test and
do have a very good Tobias TB+ densitometer. I think
the procedure will lend itself to papers.

Thorough washing out of the silver nitrate, HT-2 or similar,
test solution with out affecting the sulfide stain is the
subject of the paper; the stain being a measure of
residual fixer levels. Dan

Just to clarify, it's policy that we try to keep sponsors and their affiliates from posting in each others threads or threads regarding each others products. I saw this thread to discuss a product by pf and an affiliate (so to speak) of digialtruth responding in the thread. I will send out another round of emails to the companies to ensure everyone is up to speed regarding this. Thanks