Do the leaves of rhubarb (Rheum rhabarbarum) contain more oxalic acid than the
stems?

Rhubarb (Rheum rhabarbarum) is a stalk fruit which we consume cooked in various forms,
probably most famously with custard. The acidity has always been apparent when eating the
fruit and many people know the old wives’ tale that you must not eat the leaves. For example,
the Good Housekeeping cookery book1 states: “The leaves of rhubarb must not be eaten as
they are poisonous.” My father grows rhubarb in the garden and I like cooking so the aim of this
investigation is to find evidence to support the fact that the leaves are more poisonous than the
stems.

When looking up the composition of rhubarb2 one of the major components is oxalic acid which I
know to be poisonous from an earlier school practical entitled: ‘Acid-base reactions’3 This aimed
to find the number of moles of water of crystallisation in crystals of oxalic acid, (COOH)2.xH2O
by titration with a standard solution of sodium hydroxide.

As well as oxalic acid, rhubarb contains many other ingredients. The principal ones are gallic
acid, rheidine, sennidine, tannins, pectin, resin and starch2. However it does appear that among
these oxalic acid is the only substance present in enough quantity to be the main poison.
Because my total time for the investigation is limited to ten hours I decided to focus on the
specific research question:

Do the leaves of rhubarb (Rheum rhabarbarum) contain more oxalic acid than the
stems?

Oxalic acid has the IUPAC name ethanedioic acid. It is a diprotic acid with the formula HOOC-
COOH. Its physical properties include:

1. It melts at 185 oC4 and exists as dihydrated crystals at room temperature.

2. It is soluble in water to the extent of 9 g in 100 g of water at 20 oC.
3. It decomposes above 150 oC in accordance with the equation below:

HOOC-COOH → HCOOH + CO2

It has several harmful effects on humans, the principal one being that it causes kidney failure
due to the precipitation of calcium oxalate (the main constituent of kidney stones)2.

I considered two possible methods to achieve my aim of discovering the percentage of oxalic
acid in both the leaves and the stem.

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 1  
  
 
 
 
I. Extraction followed by gravimetric analysis
Record the original mass of both the leaf and the stalk. Then extract the oxalic acid, find its
mass and hence the percentage.

II. Titration
The oxalic acid content can be obtained either by acid-base titration or by redox titration.
However the results would be affected either by other acids present in the rhubarb or by the
presence of other oxidisable substances.

Looking at the two methods it is clear that there is no easy form of extraction to obtain complete
and pure oxalic acid. The second method of titrating the acid looked to be preferable. This has
the advantage that the percentage of oxalic acid in the leaves and stems can be arrived at by
two different titration methods (acid-base and redox) and the two methods compared to see
which is more accurate. The major assumptions that have to made are that no other acids or
oxidisable substances interfere with the results and that all the oxalic acid in both the leaves and
stems reacts during the titration reactions.

Safety precautions
When working in the laboratory safety glasses and a protective laboratory coat were worn.
Oxalic acid is clearly poisonous so care was taken not to ingest it and hands were washed at
the end of every session. Normal safety precautions were taken when handling hot objects,
glassware and chemicals such as dilute solutions of sodium hydroxide and potassium
managanate(VII) and 1.00 mol dm-3 sulfuric acid.

Drying and determining the percentage of water in the rhubarb.

By first removing the water from the rhubarb I could find the percentage of oxalic acid in the dry
masses and (by multiplying by the water ratio) in the normal masses of both the leaves and the
stems. I felt that it would be easier to carry out the titrations using the dry masses, as the
concentration would be greater making the uncertainty much smaller.

On a typical summer’s day in the UK (temperature 21 oC) three stems and three leaves of
rhubarb were picked from the garden. The stems were between 35 and 40 cm long and the
leaves ranged between 65 and 72 cm across at their broadest part. The leaves and stems were
then cleaned with water so that all the dirt was removed. The water was wiped off with some
kitchen towel so that the rhubarb had no excess substances on its surface. Two pyrex bowls
were weighed and the leaves placed in one bowl and the stems in the other. The mass of the
stems and leaves was then recorded before being placed in an oven. The oven was set at 120
o
C because at temperatures above 150 oC the oxalic acid in the rhubarb would decompose. It
was left in the oven for two days to remove any trace of water. Initially the rhubarb stems were
red and after drying both the stems and the leaves were black and much smaller.

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 2  
  
 
 
 
Mass before drying / g Mass after drying / g Mass of water removed / g
(± 0.5 g) (± 0.5 g) (± 1.0 g)

Stems 575.0 35.0 540.0

Leaves 705.0 66.5 638.5

The stems contain 93.9% water and the leaves have the slightly lower value of 90.6% with both
values having a total uncertainty of ± 0.2%.

Preparation of the stem and leaf solutions

One problem I had to overcome was to find the best way of extracting the oxalic acid from the
rhubarb in order to make a solution to titrate. I knew that oxalic acid is soluble in water so if the
acid, which is now in crystalline form, could be dissolved in water then the rest of what remained
of the rhubarb could be filtered off. The solution needed to be clear so that the titrations could
be performed otherwise there would be no need to separate the oxalic acid from the rest of the
rhubarb. The problem was to ensure that all the oxalic acid would go into solution as some
might remain with the rhubarb. To release as much acid as possible the surface area of the
rhubarb had to be as large as possible. To achieve this I crushed up the stem and then boiled
with water.

About 7 g of the dried stem was taken and placed in a mortar and pestle. It was crushed up into
very small pieces, which took quite a long time and during the process some of the stem was
lost in chunks or through dust. It was not particularly easy to crush the stem and even after a
considerable amount of time the surface area was not as large as it could have been. This may
mean that some of the oxalic acid was not extracted. 5.115 ± 0.001 g of the crushed stem was
put into a beaker. About 70 cm3 of distilled water was then added to this beaker and it was
heated and stirred constantly until it boiled. It was then filtered into a 200 cm3 volumetric flask.
There was still some solid in the beaker so that was boiled up with more distilled water and
filtered twice more to try to maximise the amount extracted. The stirring rod and the beaker
were washed into the filter paper with distilled water and then the filter paper was washed with
distilled water in to the volumetric flask. The now yellow solution in the volumetric flask was
made up to the 200 cm3 mark with distilled water and shaken.

The leaves from the rhubarb were prepared in exactly the same way as the stem.

A significant difference between the leaves and the stem was that the leaves were much easier
to crush. After about 20% of the time taken for the stem, the leaves were crushed into a fine
dust. This means the leaves had more surface area, which could mean that more of the oxalic

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 3  
  
 
 
 
acid was extracted. 5.107 ± 0.001 g of the crushed leaf was then made up to 200 cm3 of
solution using the same procedure as with the stem. The resulting solution was darker and more
orange than the yellow stem solution.

Acid-alkali titration
The equation for the reaction is:

2NaOH(aq) + HOOC-COOH(aq) → NaOOC-COONa(aq) + 2H2O(l)

To familiarise myself with this procedure and to check the experimental error in the procedure I
made up a standard solution of oxalic acid by dissolving a known mass of dihydrated oxalic acid
crystals in water and transferring the solution together with all the washings into a volumetric
flask and making the total volume up to 200 cm3 with distilled water. A small amount of a
standard solution sodium hydroxide with a concentration of 0.100 mol dm-3 (prepared by the
technician) was used to rinse a burette. The burette was then filled to a certain level with the
NaOH(aq) solution and the volume noted. 10.0 cm3 of the oxalic acid solution was pipetted into
a conical flask with two drops of phenolphthalein indicator. The sodium hydroxide solution was
added to the conical flask until one drop caused the colour of the solution to turn permanently to
faint pink and the volume recorded. The method was found to be accurate to within 1% of the
expected result, which means that I could assume the technician made up the sodium hydroxide
solution accurately.

Using the same procedure, 10.0 cm3 of the stem solution and 10.0 cm3 of the leaf solution were
both titrated three times each to give an average result.

Stem:

Rough 1st accurate 2nd accurate

Initial burette / cm3 0.00 3.15 6.15

Final burette / cm3 3.15 6.15 9.15

Volume used / cm3 3.15 3.00 3.00

Average volume used = 3.00 cm3

3.00 cm3 of 0.100 mol dm-3 NaOH(aq) was required to react exactly with 10.0 cm3 of the stem
solution.

Hydrogen ion concentration in the stem solution = 0.0300 mol dm-3.

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 4  
  
 
 
 

Leaves:

Rough 1st accurate 2nd accurate

Initial burette / cm3 0.00 3.85 7.45

Final burette / cm3 3.85 7.45 11.10

Volume used / cm3 3.85 3.60 3.65

Average volume used = (3.60 + 3.65) / 2 = 3.63 cm3

3.63 cm3 of 0.100 mol dm-3 NaOH(aq) was required to react exactly with 10.0 cm3 of the stem
solution.

Hydrogen ion concentration in the leaf solution = 0.0363 mol dm-3.

Uncertainties:
Mass of oxalic acid (± 0.001 g): % uncertainty = (0.001 / 5.115) x 100 = 0.02%
200 cm3 Volumetric flask (± 0.1 cm3): % uncertainty = (0.1 / 200) x 100 = 0.05%
10.0 cm3 pipette (± 0.05 cm3): % uncertainty = (0.05 / 10.0) x 100 = 0.5%
20.0 cm3 burette (± 0.05 cm3): % uncertainty = (0.05 / 3.00) x 100 = 1.7%
Total percentage uncertainty = 2.3%1

Hydrogen ion concentration in the stem solution = 0.0300 ± 0.007 mol dm-3.
Hydrogen ion concentration in the leaf solution = 0.0363 ± 0.008 mol dm-3.

Redox titration
To check experimental error and familiarise myself with the procedure, I used the same
standard oxalic acid solution prepared for the acid-base reaction and performed a redox titration
with 0.0200 mol dm-3 potassium manganate(VII) solution in acidic solution.
                                                                                                                       
1
 Since the mass of the leaves (5.107 g) was almost the same as the stem mass and the average volume
3
required to titrate the leaves solution (3.63 cm ) was almost the same as the average volume to titrate
the stem solution, I have assumed the same percentage uncertainty in each case.  
 
 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 5  
  
 
 
 
The equation for the reaction is:

5HOOC-COOH(aq) + 2MnO4−(aq) + 6H+(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O(l)

This is an example of an autocatalytic reaction5 with the manganese(II) ion formed as one of the
products catalysing the reaction. 10.0 cm3 of the oxalic acid solution was pipetted into a conical
flask and an extra 10.0 cm3 of 1.0 mol dm-3 sulfuric acid added. This was then heated to 60 oC
and titrated with the potassium manganate(VII) solution. Once the reaction had started it was no
longer necessary to heat the reaction mixture due to the autocatalysis. Because the potassium
manganate(VII) solution was so dark I took readings from the top of the meniscus rather than
the bottom. The end-point was taken when one drop caused a permanent faint pink colour to
remain. Again the percentage error was found to be within 1%.

When the experiment was carried out with both the stem solution and the leaf solution the
procedure would appear to be more unreliable because the solution did not sharply turn light
pink. As more manganate(VII) ions were added the solution turned darker and darker so that no
sudden change to pink could be seen. The manganate(VII) ions would also turn the solution
dark pink and then return after a period of time to its previous colour. A best guess had to be
made from these findings and I think the error could be quite large.

Stem:

Rough 1st accurate 2nd accurate

Initial burette / cm3 0.00 0.00 0.00

Final burette / cm3 12.75 12.35 12.45

Volume used / cm3 12.75 12.35 12.45

Average volume used = 12.40 cm3

12.40 cm3 of 0.0200 mol dm-3 MnO4−(aq) was required to react exactly with 10.0 cm3 of the stem
solution.

Amount of MnO4− required = (12.40 / 1000) x 0.0200 = 2.48 x 10-4 mol.

Amount of oxalic acid in 10.0 cm3 = 5/2 x 2.48 x 10-4 = 6.20 x 10-4 mol.
Concentration of oxalic acid in the stem solution = 0.0620 mol dm-3.

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 6  
  
 
 
 

Leaves:

Rough 1st accurate 2nd accurate

Initial burette / cm3 0.00 0.00 0.00

Final burette / cm3 10.20 10.05 10.00

Volume used / cm3 10.20 10.05 10.00

Average volume used = 10.03 cm3.

10.03 cm3 of 0.0200 mol dm-3 MnO4−(aq) was required to react exactly with 10.0 cm3 of the stem
solution.

Amount of MnO4− required = (10.03 / 1000) x 0.0200 = 2.01 x 10-4 mol.

Amount of oxalic acid in 10.0 cm3 = 5/2 x 2.01 x 10-4 = 5.02 x 10-4 mol.
Concentration of oxalic acid in the leaf solution = 0.0502 mol dm-3.

Uncertainties:
Mass of oxalic acid (± 0.001 g): % uncertainty = (0.001 / 5.115) x 100 = 0.02%
200 cm3 Volumetric flask (± 0.1 cm3): % uncertainty = (0.1 / 200) x 100 = 0.05%
10.0 cm3 pipette (± 0.05 cm3): % uncertainty = (0.05 / 10.0) x 100 = 0.5%
20.0 cm3 burette (± 0.05 cm3): % uncertainty = (0.05 / 10.03) x 100 = 0.5%
Total percentage uncertainty = 1.1%2

Oxalic acid concentration in the stem solution = 0.0620 ± 0.007 mol dm-3.
Oxalic acid concentration in the leaf solution = 0.0502 ± 0.006 mol dm-3.

                                                                                                                       
2
As before with the acid-base titration method the uncertainty for both the stem and the leaves are taken
to be the same for the redox titration method.
 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 7  
  
 
 
 
Analysis of results
The table below summarises the results obtained.

[oxalic acid] [oxalic acid]

[H+(aq)] / mol dm-3 / mol dm-3
/ mol dm-3 (assumes all the acid present (assumes all oxidisable
to be oxalic acid) material to be oxalic acid)

Stem solution 0.0300 ± 0.007 0.0150 ± 0.007 0.0620 ± 0.007

Leaf solution 0.0363 ± 0.008 0.0182 ± 0.008 0.0502 ± 0.006

What is not shown here are the masses of dried leaf and stem used to make the two solutions.
Because the 5.115 g mass of the dried stem is slightly larger by 0.2% than the 5.107 g mass of
the dried leaf to compare the results the stem solution the values need to be reduced very
slightly. The difference is so small that it makes no significant difference to the outcome, so it
will be ignored.

What it does show is that the percentage of acid is higher in the dried leaves than in the dried
stem. However the results are inconclusive concerning the oxalic acid content.

1. The redox reaction shows that there is more oxidisable material in the dried stem
than in the dried leaf. If this is all assumed to be oxalic acid (which is not possible as
it is higher than the acid base result) then the old wives’ tale is incorrect.

2. Although there is more acid in the dried leaves there is more oxidisable material in
the dried stem.

3. There is, in both cases, a much larger amount of oxidisable material than there is
acid. It is of course possible that some of this oxidisable material is oxalic acid in the
form of oxalate ions rather than the free acid.

From these results some conclusions can be drawn. Either there is a large error in the
experimental procedure or there are other acids and oxidisable substances in greater
proportions than expected that are interfering with the assay for oxalic acid.

Although I have commented before on some problems with the procedure, mainly the difficulty
with the colour change, I do not think that the error caused by this could be large enough to give
such unexpected results. When repeating the titration experiments for accuracy the 1st accurate
results were similar to the 2nd accurate results showing that the values for separate reactions
were not diverse.

This must mean therefore that there are other substances in too large proportions to make this
 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 8  
  
 
 
 
procedure valid when testing for concentration of oxalic acid. Although there is more acid in the
dried leaves there is more oxidisable material in the dried stem and it is likely that there is one
(or more) non-acidic substance being oxidised. There is then more likely to be more oxalic acid
in the leaves than the stem, which supports the old wives’ tale.

What needs to be found is a way of distinguishing between the oxalic acid and the oxidisable
substances. One way of doing this would be to first of all perform the redox reaction and then
with the same solution perform the sodium hydroxide titration. Performing the redox reaction
would oxidise all the oxalic acid so that it is unable to react with the sodium hydroxide. The
amount of acid that reacted with the sodium hydroxide this time could be subtracted from the
amount of acid that reacted from the earlier acid-base titration and the result could be taken to
be the oxalic acid present. The problem with this is that it is not possible to perform easily.
Firstly the redox reaction would leave the solution pink and so it would not be possible to see
the colour change due to the phenolphthalein indicator. Secondly, the sulfuric acid used to
protonate the reaction is not all used up and so would react with the hydroxide ions.

What I did do was to perform the reaction the other way round. First performing the titration with
sodium hydroxide and then doing the redox reaction with the same solution. This would not only
give me a value for oxalic acid content but it should also show the amount of oxidisable material
since the oxalic acid changes to sodium oxalate when reacted with sodium hydroxide and both
oxalic acid and oxalate ions are oxidisable substances.

This reaction was performed with the leaf solution using the same procedures as before but
both combined. As before, the hydrogen ion concentration was found to be 0.036 mol dm-3. The
redox reaction only required an average of 9.00 cm3 of the manganate solution compared with
the previous value of 10.03 cm3. This gives an ‘oxalic’ acid concentration of 0.045 mol dm-3.
Although there is a small change (approximately) 10%) it does suggest that most of the acid in
the leaf solution is oxidisable and therefore likely to be mainly oxalic acid.

In the Rhubarb compendium2 it states that rhubarb contains between 0.39 – 0.54% oxalic acid
in the stem, of which 0.23 – 0.32% is water-soluble. The corresponding figures for the leaves
are 0.59 - 0.72% and 0.46 – 0.51%. My results for the mass percentage in the original stems
and leaves (before the water was removed) can be worked out as follows:

For the stem using the oxalic acid concentration determined from the acid-base titration.
Mass of dried stem residue made up to 200 cm3 = 5.115 g
Original mass of stem before drying made up to 200 cm3 = 5.115 x (575.0 / 35.0) = 84.032 g
Concentration of oxalic acid found = 0.0150 mol dm-3
Amount of oxalic acid in 200 cm3 = amount of oxalic acid in stem = 0.0150 x (200 / 1000)
= 0.00300 mol
M oxalic acid = (2 x 12.01) + (4 x 16.00) + (2 x 1.01) = 90.04 g mol-1

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 9  
  
 
 
 
Mass of oxalic acid in stem = 90.04 x 0.00300 = 0.27 g
% by mass of oxalic acid in stem = (0.27 / 84.032) x 100 = 0.32%.

This value is lower than the total amount claimed in the literature to be present in the stem but is
exactly the same as the upper limit (0.32%) reported for the amount of soluble oxalic acid in the
stem.

By following similar calculations the percentage amounts for all the different methods are shown
below and compared with the literature values.

% by mass of % by mass of oxalic % by mass of oxalic acid

oxalic acid acid determined by - literature value
determined by redox titration
acid-base titration Water soluble total

Stem 0.32 1.33 0.23 - 0.32 0.39 - 0.54

Leaves 0.61 1.67 0.46 - 0.51 0.59 - 0.72

The comparison of the results obtained with the literature values confirms that other acids and
other oxidisable material in addition to oxalic acid are present in rhubarb. Because the literature
values are given as a range it is not particularly helpful to calculate the percentage errors. The
acid-base results tend to suggest that other acids are not making a large difference to the result
but the amount of other oxidisable material does significantly affect the redox experimental
method. Note too that, although the concentration of oxalic acid in the solution made from the
dried leaves was less than in the dried stem solution, when the percentages by mass of oxalic
acid in the original leaves and in the original stem are calculated, the leaves have the higher
value.

Conclusion

Although the old wives’ tale stated at the beginning of this investigation, i.e. that the leaves
should not be eaten as they are poisonous (because they contain more oxalic acid than the
stems), is not fully supported by the results, what I have learned is the difficulty of finding a
suitable method to obtain reliable results within the short time period of ten hours.

The method I followed had one vital assumption that proved to be of significant importance to
cause the results to be invalid. This was the fact that there were no other oxidisable materials in
the procedure that could react with the acidified manganate(VII) ions in the redox titration. The
general conclusion that can be drawn from the results is that there is approximately twice as

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 10  
  
 
 
 
much acid in the original leaves compared to the stem (0.61% compared to 0.32% by mass),
and that there is more oxidisable material in the original leaves compared to the stem (1.67%
compared to 1.33% by mass).

The experimental methods themselves were shown to work well when pure oxalic acid was
used but errors were introduced when it came to determining the exact point at which all the
substances had reacted when the oxalic acid solution from the rhubarb was used. Although a
white tile was put under the conical flask it was still difficult to determine the exact point at which
the colour changed during the redox reaction. This was a practical difficulty. A further problem,
which has not been investigated, is how much of the oxalic present was actually transferred to
the aqueous solution and how much remained in the rhubarb. From the literature values it is
clear that some of the oxalic acid is water insoluble so my results are probably lower than the
true value, not withstanding that they may also include other acids and oxidisable material.

Future work

There is obviously scope to investigate further whether other acids and oxidisable material are
also extracted into the aqueous solution along with the oxalic acid. One experiment that could
be done in a school laboratory is to perform thin layer chromatography on the extracted
samples. Once a suitable eluent has been found the spots could be developed either using
iodine or ultraviolet light. This would determine whether other components are present although
is unlikely to aid identification. Although not possible in our school laboratory, the sample could
also be subjected to gas liquid chromatography or high performance liquid chromatography
followed by mass spectral analysis, which would enable other components to be positively
identified.

Because this investigation was limited to ten hours only three samples of rhubarb were used
and these all came from the same plant on the same day. The fact that the literature gives a
range of values for the percentage of oxalic acid in the leaves and stems suggests that it may
vary from plant to plant. It may also vary according to the time of year as rhubarb is often
‘forced’ early in the season and frost may have an effect. With more time, samples taken
throughout the year and from different varieties should also be investigated.

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 11  
  
 
 
 

Bibliography

1. Good Housekeeping Institute (comp) (2004), Good Housekeeping Cookery Book (6th. Ed.),
London, Collins & Brown.

2. The Rhubarb Compendium (2010), [Online] Available: http://www.rhubarbinfo.com/poison [2

August 2015].

3. Neuss G. (2014), Acid-base titrations, InThinking Chemistry website, [Online] Available:

http://www.thinkib.net/chemistry/page/16615/acid-base-titrations- [2 August 2015].

4. ChemSpider, [Online] Available: http://www.chemspider.com/Chemical-Structure.946.html [3

August 2015].

5. Clugston M. & Flemming R. (2013), Advanced Chemistry (2nd Ed.), Oxford, Oxford University
Press.

 
 
  Dr Geoffrey Neuss, InThinking
©
 http://www.thinkib.net/chemistry 12