Ripper Titration So2

https://vinmetrica.
com/the-ripper-titration-recent-improvements-in-measuring-so2/
There are Several Approaches one can take to determine free SO2. However, as a large number
of winemakers rely on the simple Ripper titration, we thought it a good idea to elaborate on the
virtues and cautions of using this method.
In the Ripper titration, standard iodine is titrated into an acidified wine sample. The iodine
reacts with free SO2, and when the SO2 has all been titrated, free iodine appears at the
endpoint. Originally described in 18981, the original Ripper method is fast but its accuracy and
precision are notably poor, primarily because it relies on the appearance of a dark blue starch-
iodine complex to detect the end point, which is difficult to see (especially in red wines) and
subject to errors of interpretation2.
However, the method’s speed and simplicity are attractive; many winemakers have claimed
that they can train themselves to read the endpoint reproducibly.
Some modifications to the Ripper method improve the reliability of detecting the endpoint. For
example, the use of electrochemical sensors that respond to the appearance of free iodine
removes the burden of trying to visualize the starch endpoint against a dark background in red
wines.
There have been numerous reports describing the various sources of potential error and
interferences in the Ripper method. The acidification step (also required in some other
methods) induces slow dissociation of bound SO2 to form more free SO2, leading to a
systematic overestimation of free SO2. This effect can be minimized by performing the Ripper
titration quickly (within 2 minutes), such that it probably contributes less than a few percent
error.
Another source of error that can lead to overestimation of free SO2 is the presence of other
oxidizable compounds in the wine. These can react with the iodine titrant, again leading to
overestimation of the SO2 level. In some white wines, there are appreciable levels of ascorbic
acid which react readily with the titrant. In red wines, the presence of phenolic compounds can
also lead to overestimation.
In this case the error may be estimated by a modified Ripper method 3 in which duplicate
samples are titrated, one having been pretreated with a drop of 3% hydrogen peroxide, the
other untreated. The difference between the two values provides an estimate of the “true” SO2
ppm value (since peroxide primarily removes only the free SO2).
Indeed, the aeration oxidation (AO) method, which is theoretically free of these interferences,
has been shown in one independent study to give identical results to those of the SC-100 4 .
Although it seems to be generally accepted that Ripper methods produce higher values and are
less accurate5 than other methods, it is possible that the Vinmetrica’s improved endpoint
detection may change this perception
In summary, the Ripper method is quick and can be made reliable and accurate enough to guide
the winemaker in maintaining proper levels of sulfur dioxide. The SC-100A and SC-300 are
simple and inexpensive SO2 meters for accurate SO2 analysis.
Other references:
A summary of an ASEV meeting discussing a comparison of methods
Capillary electrophoresis vs. AO vs. Ripper
More SO2 stuff; good overview.
1 M. Ripper, Die Schwelflige Saure im Wein und deren Bestimmung, J. Praia. Chem. 46, 428-73
(1898)
2 James E Vahl and Jean E. Converse, Ripper procedure for determining sulfur dioxide in Wine:
Collaborative study. J Assoc Off Anal Chem 63, 194-9 (1980)
3 http://www.gencowinemakers.com/docs/Measuring%20Free%20Sulfur%20Dioxide.pdf
4 https://vinmetrica.com/Souder_Eval.pdf
5 J.W. Buechsenstein and C. S. Ough, SO2 Determination by Aeration-Oxidation: A Comparison

with Ripper (1978) Am. J. Enol. Vitic. 29:3:161-164
Fred
March 29, 2017
The article states that when performing the modified Ripper method a drop of 3% hydrogen peroxide is used to
treat the sample. This modified method’s reference is a procedure prepared by Lum Eisenman. But Eisenman
never mentions how much hydrogen peroxide to use when treating the sample. Is there another reference for
this? How do you know that one drop is enough?
Richard Sportsman
April 3, 2017
Fred,
I actually got this recipe from Lum himself, so I don’t have an independent reference for it. But it makes sense: 1
drop of 3% peroxide (H2O2) is about the equivalent of 6 mL of the SO2 Titrant that we provide [If one drop is about
0.05 mL, and 3% H2O2 is about 2 molar, then each drop is about 0.1 mmol of H2O2. Each mmol of H2O2 reacts
with one mmol of SO2, so this equals 0.1 mmol of SO2. Each mmol SO2 reacts with one meq of the SO2 titrant,
whose strength is 0.0156 meq/ml. So you have 0.1 meq/0.0156 = ~ 6 mL]. So unless your original titration was
more than 6 mL, one drop should be enough. You can add 2 if you want.
casvesve
September 24, 2012
I have just ordered a SC 300 instrument. As I am an international customer the 2 M HCl will not be part of the kit. I
have a supplier of kit for SO2 test for the Ripper method and this kit contains H2SO4 instead. Does is make a
difference to the instrument?
Sveneric Svensson
Dr. Richard Sportsman
September 24, 2012
You can use sulfuric acid in place of HCl if the sulfuric is known to be suitable for Ripper use.
Best regards,
Rich

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5 J.W. Buechsenstein and C. S. Ough, SO2 Determination by Aeration-Oxidation: A Comparison

March 29, 2017

September 24, 2012

Dr. Richard Sportsman

September 24, 2012

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