Is oxalic acid dihydrate considered a primary acid standard in analytical chemistry? The Next CEO of Stack OverflowHow to standardise NaOH?What are the limits of analytical chemistry?Oxalic acid structureHow to determine amount of CO₂ in soda waterDefinition of major, minor, and trace elements in analytical chemistryHow do I calculate the concentration of sulphuric acid by a titration experiment with sodium hydroxide?Analytical Chemistry Textbook RecommendationConcentrating Oxalic Acid by Evaporationanalytical chemistry standard deviationWhat primary standard acid can be used to standardise NaOH solutions by titration?Calculation of composition of drain cleaner

Describing a person. What needs to be mentioned?

What is the point of a new vote on May's deal when the indicative votes suggest she will not win?

When Does an Atlas Uniquely Define a Manifold?

Does the Brexit deal have to be agreed by both Houses?

MAZDA 3 2006 (UK) - poor acceleration then takes off at 3250 revs

How can I quit an app using Terminal?

How do I go from 300 unfinished/half written blog posts, to published posts?

Is it safe to use c_str() on a temporary string?

How to be diplomatic in refusing to write code that breaches the privacy of our users

Rotate a column

How did people program for Consoles with multiple CPUs?

How do spells that require an ability check vs. the caster's spell save DC work?

How do scammers retract money, while you can’t?

Is it my responsibility to learn a new technology in my own time my employer wants to implement?

What is the purpose of the Evocation wizard's Potent Cantrip feature?

How easy is it to start Magic from scratch?

When airplanes disconnect from a tanker during air to air refueling, why do they bank so sharply to the right?

What does "Its cash flow is deeply negative" mean?

Need some help with wall behind rangetop

Should I tutor a student who I know has cheated on their homework?

What can we do to stop prior company from asking us questions?

Whats the best way to handle refactoring a big file?

Trouble understanding the speech of overseas colleagues

Anatomically Correct Mesopelagic Aves



Is oxalic acid dihydrate considered a primary acid standard in analytical chemistry?



The Next CEO of Stack OverflowHow to standardise NaOH?What are the limits of analytical chemistry?Oxalic acid structureHow to determine amount of CO₂ in soda waterDefinition of major, minor, and trace elements in analytical chemistryHow do I calculate the concentration of sulphuric acid by a titration experiment with sodium hydroxide?Analytical Chemistry Textbook RecommendationConcentrating Oxalic Acid by Evaporationanalytical chemistry standard deviationWhat primary standard acid can be used to standardise NaOH solutions by titration?Calculation of composition of drain cleaner










7












$begingroup$


Using oxalic acid dihydrate as a primary standard just seems really odd to me. I'd expect a primary standard to be oven dried. It just seems weird that a hydrate would be used.



Granted, I saw numerous references to using oxalic acid dihydrate on the web to standardize $ceNaOH$. I assume that for high school and freshman labs that it is "good enough." Using student grade burettes and open air pan balances would greatly limit the possible precision.



Also I'd guess that "good enough purity" oxalic acid dihydrate can be purchased much more cheaply than potassium hydrogen phthalate (KHP), which would be my choice.




The analytical method as I remember from nearly 50 years ago...



Prepare a concentrated stock solution (4 molar?) of $ceNaOH$ using distilled water. That went in a jug with a spout just above the bottom. It was capped with a dedicator tube filled with $ceNaOH$ to absorb $ceCO2$ from the atmosphere. It sat for a couple of days to allow sodium carbonate to settle out. ($ceNaOH$ will have some carbonate.)



Dried KHP in an oven at $pu120 ^circC$ for four hours and then put that in a desiccator to cool.



Boiled distilled water to remove dissolved $ceCO2$ and stoppered that to cool.



Using the cooled boiled distilled water made an approximately $pu0.1 M$ solution of $ceNaOH$ by diluting the concentrated stock solution.



Using an analytical balance, weigh out 3 samples of KHP to nearest $pu0.0001 g$ into flasks and carefully dissolved the KHP in the cooled boiled distilled water with swirling to minimize introducing bubbles into the solution.



Then using $ceNaOH$ as the titrant, phenolphthalein was used as the indicator. Again careful to swirl solution, not shake, to prevent bubbles.



Using class 1 50-mL burette which was marked to $pu0.1 mL$s but read to $pu0.01 mL$.










share|improve this question











$endgroup$











  • $begingroup$
    Note that it is used also as a standard in manganometry.
    $endgroup$
    – Poutnik
    yesterday










  • $begingroup$
    Having one chemical that can be used in multiple ways would be good for cutting costs. But I'd expect that sodium oxalate would be a better redox standard than oxalic acid dihydrate.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    Perhaps sodium oxalate, yes. Btw, we had at high school analytical scales with 0.1 mg resolution, with putting a wire on the scale shoulders, reading the pointer on enlighten scale.
    $endgroup$
    – Poutnik
    yesterday







  • 1




    $begingroup$
    DAB (Deutsches Arzneibuch) lists a total of eight "Urtitersubstanzen" (= recommended primary standards), plus a dozen more which I might (for lack of a better word) call subprime standards. KHP is among the former, oxalic acid the latter.
    $endgroup$
    – Karl
    yesterday
















7












$begingroup$


Using oxalic acid dihydrate as a primary standard just seems really odd to me. I'd expect a primary standard to be oven dried. It just seems weird that a hydrate would be used.



Granted, I saw numerous references to using oxalic acid dihydrate on the web to standardize $ceNaOH$. I assume that for high school and freshman labs that it is "good enough." Using student grade burettes and open air pan balances would greatly limit the possible precision.



Also I'd guess that "good enough purity" oxalic acid dihydrate can be purchased much more cheaply than potassium hydrogen phthalate (KHP), which would be my choice.




The analytical method as I remember from nearly 50 years ago...



Prepare a concentrated stock solution (4 molar?) of $ceNaOH$ using distilled water. That went in a jug with a spout just above the bottom. It was capped with a dedicator tube filled with $ceNaOH$ to absorb $ceCO2$ from the atmosphere. It sat for a couple of days to allow sodium carbonate to settle out. ($ceNaOH$ will have some carbonate.)



Dried KHP in an oven at $pu120 ^circC$ for four hours and then put that in a desiccator to cool.



Boiled distilled water to remove dissolved $ceCO2$ and stoppered that to cool.



Using the cooled boiled distilled water made an approximately $pu0.1 M$ solution of $ceNaOH$ by diluting the concentrated stock solution.



Using an analytical balance, weigh out 3 samples of KHP to nearest $pu0.0001 g$ into flasks and carefully dissolved the KHP in the cooled boiled distilled water with swirling to minimize introducing bubbles into the solution.



Then using $ceNaOH$ as the titrant, phenolphthalein was used as the indicator. Again careful to swirl solution, not shake, to prevent bubbles.



Using class 1 50-mL burette which was marked to $pu0.1 mL$s but read to $pu0.01 mL$.










share|improve this question











$endgroup$











  • $begingroup$
    Note that it is used also as a standard in manganometry.
    $endgroup$
    – Poutnik
    yesterday










  • $begingroup$
    Having one chemical that can be used in multiple ways would be good for cutting costs. But I'd expect that sodium oxalate would be a better redox standard than oxalic acid dihydrate.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    Perhaps sodium oxalate, yes. Btw, we had at high school analytical scales with 0.1 mg resolution, with putting a wire on the scale shoulders, reading the pointer on enlighten scale.
    $endgroup$
    – Poutnik
    yesterday







  • 1




    $begingroup$
    DAB (Deutsches Arzneibuch) lists a total of eight "Urtitersubstanzen" (= recommended primary standards), plus a dozen more which I might (for lack of a better word) call subprime standards. KHP is among the former, oxalic acid the latter.
    $endgroup$
    – Karl
    yesterday














7












7








7


1



$begingroup$


Using oxalic acid dihydrate as a primary standard just seems really odd to me. I'd expect a primary standard to be oven dried. It just seems weird that a hydrate would be used.



Granted, I saw numerous references to using oxalic acid dihydrate on the web to standardize $ceNaOH$. I assume that for high school and freshman labs that it is "good enough." Using student grade burettes and open air pan balances would greatly limit the possible precision.



Also I'd guess that "good enough purity" oxalic acid dihydrate can be purchased much more cheaply than potassium hydrogen phthalate (KHP), which would be my choice.




The analytical method as I remember from nearly 50 years ago...



Prepare a concentrated stock solution (4 molar?) of $ceNaOH$ using distilled water. That went in a jug with a spout just above the bottom. It was capped with a dedicator tube filled with $ceNaOH$ to absorb $ceCO2$ from the atmosphere. It sat for a couple of days to allow sodium carbonate to settle out. ($ceNaOH$ will have some carbonate.)



Dried KHP in an oven at $pu120 ^circC$ for four hours and then put that in a desiccator to cool.



Boiled distilled water to remove dissolved $ceCO2$ and stoppered that to cool.



Using the cooled boiled distilled water made an approximately $pu0.1 M$ solution of $ceNaOH$ by diluting the concentrated stock solution.



Using an analytical balance, weigh out 3 samples of KHP to nearest $pu0.0001 g$ into flasks and carefully dissolved the KHP in the cooled boiled distilled water with swirling to minimize introducing bubbles into the solution.



Then using $ceNaOH$ as the titrant, phenolphthalein was used as the indicator. Again careful to swirl solution, not shake, to prevent bubbles.



Using class 1 50-mL burette which was marked to $pu0.1 mL$s but read to $pu0.01 mL$.










share|improve this question











$endgroup$




Using oxalic acid dihydrate as a primary standard just seems really odd to me. I'd expect a primary standard to be oven dried. It just seems weird that a hydrate would be used.



Granted, I saw numerous references to using oxalic acid dihydrate on the web to standardize $ceNaOH$. I assume that for high school and freshman labs that it is "good enough." Using student grade burettes and open air pan balances would greatly limit the possible precision.



Also I'd guess that "good enough purity" oxalic acid dihydrate can be purchased much more cheaply than potassium hydrogen phthalate (KHP), which would be my choice.




The analytical method as I remember from nearly 50 years ago...



Prepare a concentrated stock solution (4 molar?) of $ceNaOH$ using distilled water. That went in a jug with a spout just above the bottom. It was capped with a dedicator tube filled with $ceNaOH$ to absorb $ceCO2$ from the atmosphere. It sat for a couple of days to allow sodium carbonate to settle out. ($ceNaOH$ will have some carbonate.)



Dried KHP in an oven at $pu120 ^circC$ for four hours and then put that in a desiccator to cool.



Boiled distilled water to remove dissolved $ceCO2$ and stoppered that to cool.



Using the cooled boiled distilled water made an approximately $pu0.1 M$ solution of $ceNaOH$ by diluting the concentrated stock solution.



Using an analytical balance, weigh out 3 samples of KHP to nearest $pu0.0001 g$ into flasks and carefully dissolved the KHP in the cooled boiled distilled water with swirling to minimize introducing bubbles into the solution.



Then using $ceNaOH$ as the titrant, phenolphthalein was used as the indicator. Again careful to swirl solution, not shake, to prevent bubbles.



Using class 1 50-mL burette which was marked to $pu0.1 mL$s but read to $pu0.01 mL$.







acid-base analytical-chemistry






share|improve this question















share|improve this question













share|improve this question




share|improve this question








edited yesterday









Mathew Mahindaratne

1,74013




1,74013










asked yesterday









MaxWMaxW

15.2k22261




15.2k22261











  • $begingroup$
    Note that it is used also as a standard in manganometry.
    $endgroup$
    – Poutnik
    yesterday










  • $begingroup$
    Having one chemical that can be used in multiple ways would be good for cutting costs. But I'd expect that sodium oxalate would be a better redox standard than oxalic acid dihydrate.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    Perhaps sodium oxalate, yes. Btw, we had at high school analytical scales with 0.1 mg resolution, with putting a wire on the scale shoulders, reading the pointer on enlighten scale.
    $endgroup$
    – Poutnik
    yesterday







  • 1




    $begingroup$
    DAB (Deutsches Arzneibuch) lists a total of eight "Urtitersubstanzen" (= recommended primary standards), plus a dozen more which I might (for lack of a better word) call subprime standards. KHP is among the former, oxalic acid the latter.
    $endgroup$
    – Karl
    yesterday

















  • $begingroup$
    Note that it is used also as a standard in manganometry.
    $endgroup$
    – Poutnik
    yesterday










  • $begingroup$
    Having one chemical that can be used in multiple ways would be good for cutting costs. But I'd expect that sodium oxalate would be a better redox standard than oxalic acid dihydrate.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    Perhaps sodium oxalate, yes. Btw, we had at high school analytical scales with 0.1 mg resolution, with putting a wire on the scale shoulders, reading the pointer on enlighten scale.
    $endgroup$
    – Poutnik
    yesterday







  • 1




    $begingroup$
    DAB (Deutsches Arzneibuch) lists a total of eight "Urtitersubstanzen" (= recommended primary standards), plus a dozen more which I might (for lack of a better word) call subprime standards. KHP is among the former, oxalic acid the latter.
    $endgroup$
    – Karl
    yesterday
















$begingroup$
Note that it is used also as a standard in manganometry.
$endgroup$
– Poutnik
yesterday




$begingroup$
Note that it is used also as a standard in manganometry.
$endgroup$
– Poutnik
yesterday












$begingroup$
Having one chemical that can be used in multiple ways would be good for cutting costs. But I'd expect that sodium oxalate would be a better redox standard than oxalic acid dihydrate.
$endgroup$
– MaxW
yesterday




$begingroup$
Having one chemical that can be used in multiple ways would be good for cutting costs. But I'd expect that sodium oxalate would be a better redox standard than oxalic acid dihydrate.
$endgroup$
– MaxW
yesterday












$begingroup$
Perhaps sodium oxalate, yes. Btw, we had at high school analytical scales with 0.1 mg resolution, with putting a wire on the scale shoulders, reading the pointer on enlighten scale.
$endgroup$
– Poutnik
yesterday





$begingroup$
Perhaps sodium oxalate, yes. Btw, we had at high school analytical scales with 0.1 mg resolution, with putting a wire on the scale shoulders, reading the pointer on enlighten scale.
$endgroup$
– Poutnik
yesterday





1




1




$begingroup$
DAB (Deutsches Arzneibuch) lists a total of eight "Urtitersubstanzen" (= recommended primary standards), plus a dozen more which I might (for lack of a better word) call subprime standards. KHP is among the former, oxalic acid the latter.
$endgroup$
– Karl
yesterday





$begingroup$
DAB (Deutsches Arzneibuch) lists a total of eight "Urtitersubstanzen" (= recommended primary standards), plus a dozen more which I might (for lack of a better word) call subprime standards. KHP is among the former, oxalic acid the latter.
$endgroup$
– Karl
yesterday











2 Answers
2






active

oldest

votes


















4












$begingroup$

At first glance, use of oxalic acid dihydrate ($ceH2C2O4.2H2O$ or simply OADH) as a primary standard seems really odd to anybody including me (although I'm not a analytical chemist). I'd also expect a primary standard to be oven dried and cool it in desiccator before use as we all did in our college analytical lab using potassium hydrogen phthalate (KHP). Yet, there is a good reason why these chemist use OADH continuously.



When it comes to be a good primary standard, Low hygroscopicity is one of the features in consideration, in order to minimize weight changes due to humidity. Oxalic acid dihydrate (OADH) and potassium hydrogen phthalate (KHP) are the most accessible acids for standardization, because of their low cost and their hardly changing content per a unit (of measurement). Specifically, OADH in the crystalline solid state, represents an interesting species that is still producing many surprises since 1920s. Although there are two extra water molecules in OADH (thich is hard to loose), the alternating acid and these water molecules act both as hydrogen-bond donors and acceptors [Ref.1]. The conclusion of that reference states that:




The trends both in the metric and electronic parameters exhibited by the model clusters with increasing the number of participating oxalic acid and water molecules (Figure 1) shows clearly that the cooperative effect is the major factor in the shortening of H-bonds. This is particularly well pronounced in the optimized $R_ceO··O$ of the carboxylic hydroxyl group bonded to the water molecules. One of the most eloquent steps in the reduction of $R_ceO··O$ is between the hydrated single molecule and the circular model consisting of two acid and two water molecules, indicating that it is the circular motif that primarily supports cooperativity. However, both the polarization evoked by the hydration of the carbonyl groups as well as the crystal field effect also contribute notably to the shortening.




OxalicAcid2H2O



This strong H-bonding make it so stable that two water molecule won't loose in ambient conditions. That's a good reason to use it as a primary standard.



Reference:



  1. J. Stare, D. Hadži, “Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies,” J. Chem. Theory Comput. 2014, 10(4), 1817–1823 (DOI: 10.1021/ct500167n).





share|improve this answer









$endgroup$












  • $begingroup$
    Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    @MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
    $endgroup$
    – Mathew Mahindaratne
    14 hours ago


















4












$begingroup$

Jander-Blasius (14. Ed., 1995) uses nonhygroscopic sodium oxalate, dried at 230-250°C (it decomposes above 250 according to wikipedia), to standardise permanganate titer solution against. They give no other recommended standard for manganometry, so I assume this is it.



I have no idea why anybody would want to use (or recommend using) the free acid instead, except perhaps to insult his first-year students' intelligence. Can't imagine it's much cheaper, in analytical grade.



For NaOH titer solution, Jander recommends using a secondary standard, e.g. HCl solution. HCl itself is standardised against freshly precipitated and dried sodium carbonate, or HgO ($ce+ 4 KI + H2O -> K2[HgI4] + 2 KOH$) dried over conc. sulfuric acid.






share|improve this answer











$endgroup$












  • $begingroup$
    Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
    $endgroup$
    – MaxW
    yesterday











  • $begingroup$
    I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
    $endgroup$
    – Karl
    yesterday










  • $begingroup$
    My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
    $endgroup$
    – MaxW
    13 hours ago










  • $begingroup$
    Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
    $endgroup$
    – Karl
    12 hours ago











Your Answer





StackExchange.ifUsing("editor", function ()
return StackExchange.using("mathjaxEditing", function ()
StackExchange.MarkdownEditor.creationCallbacks.add(function (editor, postfix)
StackExchange.mathjaxEditing.prepareWmdForMathJax(editor, postfix, [["$", "$"], ["\\(","\\)"]]);
);
);
, "mathjax-editing");

StackExchange.ready(function()
var channelOptions =
tags: "".split(" "),
id: "431"
;
initTagRenderer("".split(" "), "".split(" "), channelOptions);

StackExchange.using("externalEditor", function()
// Have to fire editor after snippets, if snippets enabled
if (StackExchange.settings.snippets.snippetsEnabled)
StackExchange.using("snippets", function()
createEditor();
);

else
createEditor();

);

function createEditor()
StackExchange.prepareEditor(
heartbeatType: 'answer',
autoActivateHeartbeat: false,
convertImagesToLinks: false,
noModals: true,
showLowRepImageUploadWarning: true,
reputationToPostImages: null,
bindNavPrevention: true,
postfix: "",
imageUploader:
brandingHtml: "Powered by u003ca class="icon-imgur-white" href="https://imgur.com/"u003eu003c/au003e",
contentPolicyHtml: "User contributions licensed under u003ca href="https://creativecommons.org/licenses/by-sa/3.0/"u003ecc by-sa 3.0 with attribution requiredu003c/au003e u003ca href="https://stackoverflow.com/legal/content-policy"u003e(content policy)u003c/au003e",
allowUrls: true
,
onDemand: true,
discardSelector: ".discard-answer"
,immediatelyShowMarkdownHelp:true
);



);













draft saved

draft discarded


















StackExchange.ready(
function ()
StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f111646%2fis-oxalic-acid-dihydrate-considered-a-primary-acid-standard-in-analytical-chemis%23new-answer', 'question_page');

);

Post as a guest















Required, but never shown

























2 Answers
2






active

oldest

votes








2 Answers
2






active

oldest

votes









active

oldest

votes






active

oldest

votes









4












$begingroup$

At first glance, use of oxalic acid dihydrate ($ceH2C2O4.2H2O$ or simply OADH) as a primary standard seems really odd to anybody including me (although I'm not a analytical chemist). I'd also expect a primary standard to be oven dried and cool it in desiccator before use as we all did in our college analytical lab using potassium hydrogen phthalate (KHP). Yet, there is a good reason why these chemist use OADH continuously.



When it comes to be a good primary standard, Low hygroscopicity is one of the features in consideration, in order to minimize weight changes due to humidity. Oxalic acid dihydrate (OADH) and potassium hydrogen phthalate (KHP) are the most accessible acids for standardization, because of their low cost and their hardly changing content per a unit (of measurement). Specifically, OADH in the crystalline solid state, represents an interesting species that is still producing many surprises since 1920s. Although there are two extra water molecules in OADH (thich is hard to loose), the alternating acid and these water molecules act both as hydrogen-bond donors and acceptors [Ref.1]. The conclusion of that reference states that:




The trends both in the metric and electronic parameters exhibited by the model clusters with increasing the number of participating oxalic acid and water molecules (Figure 1) shows clearly that the cooperative effect is the major factor in the shortening of H-bonds. This is particularly well pronounced in the optimized $R_ceO··O$ of the carboxylic hydroxyl group bonded to the water molecules. One of the most eloquent steps in the reduction of $R_ceO··O$ is between the hydrated single molecule and the circular model consisting of two acid and two water molecules, indicating that it is the circular motif that primarily supports cooperativity. However, both the polarization evoked by the hydration of the carbonyl groups as well as the crystal field effect also contribute notably to the shortening.




OxalicAcid2H2O



This strong H-bonding make it so stable that two water molecule won't loose in ambient conditions. That's a good reason to use it as a primary standard.



Reference:



  1. J. Stare, D. Hadži, “Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies,” J. Chem. Theory Comput. 2014, 10(4), 1817–1823 (DOI: 10.1021/ct500167n).





share|improve this answer









$endgroup$












  • $begingroup$
    Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    @MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
    $endgroup$
    – Mathew Mahindaratne
    14 hours ago















4












$begingroup$

At first glance, use of oxalic acid dihydrate ($ceH2C2O4.2H2O$ or simply OADH) as a primary standard seems really odd to anybody including me (although I'm not a analytical chemist). I'd also expect a primary standard to be oven dried and cool it in desiccator before use as we all did in our college analytical lab using potassium hydrogen phthalate (KHP). Yet, there is a good reason why these chemist use OADH continuously.



When it comes to be a good primary standard, Low hygroscopicity is one of the features in consideration, in order to minimize weight changes due to humidity. Oxalic acid dihydrate (OADH) and potassium hydrogen phthalate (KHP) are the most accessible acids for standardization, because of their low cost and their hardly changing content per a unit (of measurement). Specifically, OADH in the crystalline solid state, represents an interesting species that is still producing many surprises since 1920s. Although there are two extra water molecules in OADH (thich is hard to loose), the alternating acid and these water molecules act both as hydrogen-bond donors and acceptors [Ref.1]. The conclusion of that reference states that:




The trends both in the metric and electronic parameters exhibited by the model clusters with increasing the number of participating oxalic acid and water molecules (Figure 1) shows clearly that the cooperative effect is the major factor in the shortening of H-bonds. This is particularly well pronounced in the optimized $R_ceO··O$ of the carboxylic hydroxyl group bonded to the water molecules. One of the most eloquent steps in the reduction of $R_ceO··O$ is between the hydrated single molecule and the circular model consisting of two acid and two water molecules, indicating that it is the circular motif that primarily supports cooperativity. However, both the polarization evoked by the hydration of the carbonyl groups as well as the crystal field effect also contribute notably to the shortening.




OxalicAcid2H2O



This strong H-bonding make it so stable that two water molecule won't loose in ambient conditions. That's a good reason to use it as a primary standard.



Reference:



  1. J. Stare, D. Hadži, “Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies,” J. Chem. Theory Comput. 2014, 10(4), 1817–1823 (DOI: 10.1021/ct500167n).





share|improve this answer









$endgroup$












  • $begingroup$
    Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    @MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
    $endgroup$
    – Mathew Mahindaratne
    14 hours ago













4












4








4





$begingroup$

At first glance, use of oxalic acid dihydrate ($ceH2C2O4.2H2O$ or simply OADH) as a primary standard seems really odd to anybody including me (although I'm not a analytical chemist). I'd also expect a primary standard to be oven dried and cool it in desiccator before use as we all did in our college analytical lab using potassium hydrogen phthalate (KHP). Yet, there is a good reason why these chemist use OADH continuously.



When it comes to be a good primary standard, Low hygroscopicity is one of the features in consideration, in order to minimize weight changes due to humidity. Oxalic acid dihydrate (OADH) and potassium hydrogen phthalate (KHP) are the most accessible acids for standardization, because of their low cost and their hardly changing content per a unit (of measurement). Specifically, OADH in the crystalline solid state, represents an interesting species that is still producing many surprises since 1920s. Although there are two extra water molecules in OADH (thich is hard to loose), the alternating acid and these water molecules act both as hydrogen-bond donors and acceptors [Ref.1]. The conclusion of that reference states that:




The trends both in the metric and electronic parameters exhibited by the model clusters with increasing the number of participating oxalic acid and water molecules (Figure 1) shows clearly that the cooperative effect is the major factor in the shortening of H-bonds. This is particularly well pronounced in the optimized $R_ceO··O$ of the carboxylic hydroxyl group bonded to the water molecules. One of the most eloquent steps in the reduction of $R_ceO··O$ is between the hydrated single molecule and the circular model consisting of two acid and two water molecules, indicating that it is the circular motif that primarily supports cooperativity. However, both the polarization evoked by the hydration of the carbonyl groups as well as the crystal field effect also contribute notably to the shortening.




OxalicAcid2H2O



This strong H-bonding make it so stable that two water molecule won't loose in ambient conditions. That's a good reason to use it as a primary standard.



Reference:



  1. J. Stare, D. Hadži, “Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies,” J. Chem. Theory Comput. 2014, 10(4), 1817–1823 (DOI: 10.1021/ct500167n).





share|improve this answer









$endgroup$



At first glance, use of oxalic acid dihydrate ($ceH2C2O4.2H2O$ or simply OADH) as a primary standard seems really odd to anybody including me (although I'm not a analytical chemist). I'd also expect a primary standard to be oven dried and cool it in desiccator before use as we all did in our college analytical lab using potassium hydrogen phthalate (KHP). Yet, there is a good reason why these chemist use OADH continuously.



When it comes to be a good primary standard, Low hygroscopicity is one of the features in consideration, in order to minimize weight changes due to humidity. Oxalic acid dihydrate (OADH) and potassium hydrogen phthalate (KHP) are the most accessible acids for standardization, because of their low cost and their hardly changing content per a unit (of measurement). Specifically, OADH in the crystalline solid state, represents an interesting species that is still producing many surprises since 1920s. Although there are two extra water molecules in OADH (thich is hard to loose), the alternating acid and these water molecules act both as hydrogen-bond donors and acceptors [Ref.1]. The conclusion of that reference states that:




The trends both in the metric and electronic parameters exhibited by the model clusters with increasing the number of participating oxalic acid and water molecules (Figure 1) shows clearly that the cooperative effect is the major factor in the shortening of H-bonds. This is particularly well pronounced in the optimized $R_ceO··O$ of the carboxylic hydroxyl group bonded to the water molecules. One of the most eloquent steps in the reduction of $R_ceO··O$ is between the hydrated single molecule and the circular model consisting of two acid and two water molecules, indicating that it is the circular motif that primarily supports cooperativity. However, both the polarization evoked by the hydration of the carbonyl groups as well as the crystal field effect also contribute notably to the shortening.




OxalicAcid2H2O



This strong H-bonding make it so stable that two water molecule won't loose in ambient conditions. That's a good reason to use it as a primary standard.



Reference:



  1. J. Stare, D. Hadži, “Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies,” J. Chem. Theory Comput. 2014, 10(4), 1817–1823 (DOI: 10.1021/ct500167n).






share|improve this answer












share|improve this answer



share|improve this answer










answered yesterday









Mathew MahindaratneMathew Mahindaratne

1,74013




1,74013











  • $begingroup$
    Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    @MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
    $endgroup$
    – Mathew Mahindaratne
    14 hours ago
















  • $begingroup$
    Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
    $endgroup$
    – MaxW
    yesterday










  • $begingroup$
    @MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
    $endgroup$
    – Mathew Mahindaratne
    14 hours ago















$begingroup$
Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
$endgroup$
– MaxW
yesterday




$begingroup$
Interesting. I have been thinking that being hygroscopic would be much more problematic than the salt losing water. Though I know that for instance exposed copper sulfate pentahydrate tends to lose water of hydration rather than be hygroscopic. // I wonder what the relative precision would be using both KHP and OADH.
$endgroup$
– MaxW
yesterday












$begingroup$
@MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
$endgroup$
– Mathew Mahindaratne
14 hours ago




$begingroup$
@MaxW: I didn't see any comparison work during my survey. Interesting thoughts though.:-)
$endgroup$
– Mathew Mahindaratne
14 hours ago











4












$begingroup$

Jander-Blasius (14. Ed., 1995) uses nonhygroscopic sodium oxalate, dried at 230-250°C (it decomposes above 250 according to wikipedia), to standardise permanganate titer solution against. They give no other recommended standard for manganometry, so I assume this is it.



I have no idea why anybody would want to use (or recommend using) the free acid instead, except perhaps to insult his first-year students' intelligence. Can't imagine it's much cheaper, in analytical grade.



For NaOH titer solution, Jander recommends using a secondary standard, e.g. HCl solution. HCl itself is standardised against freshly precipitated and dried sodium carbonate, or HgO ($ce+ 4 KI + H2O -> K2[HgI4] + 2 KOH$) dried over conc. sulfuric acid.






share|improve this answer











$endgroup$












  • $begingroup$
    Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
    $endgroup$
    – MaxW
    yesterday











  • $begingroup$
    I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
    $endgroup$
    – Karl
    yesterday










  • $begingroup$
    My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
    $endgroup$
    – MaxW
    13 hours ago










  • $begingroup$
    Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
    $endgroup$
    – Karl
    12 hours ago















4












$begingroup$

Jander-Blasius (14. Ed., 1995) uses nonhygroscopic sodium oxalate, dried at 230-250°C (it decomposes above 250 according to wikipedia), to standardise permanganate titer solution against. They give no other recommended standard for manganometry, so I assume this is it.



I have no idea why anybody would want to use (or recommend using) the free acid instead, except perhaps to insult his first-year students' intelligence. Can't imagine it's much cheaper, in analytical grade.



For NaOH titer solution, Jander recommends using a secondary standard, e.g. HCl solution. HCl itself is standardised against freshly precipitated and dried sodium carbonate, or HgO ($ce+ 4 KI + H2O -> K2[HgI4] + 2 KOH$) dried over conc. sulfuric acid.






share|improve this answer











$endgroup$












  • $begingroup$
    Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
    $endgroup$
    – MaxW
    yesterday











  • $begingroup$
    I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
    $endgroup$
    – Karl
    yesterday










  • $begingroup$
    My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
    $endgroup$
    – MaxW
    13 hours ago










  • $begingroup$
    Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
    $endgroup$
    – Karl
    12 hours ago













4












4








4





$begingroup$

Jander-Blasius (14. Ed., 1995) uses nonhygroscopic sodium oxalate, dried at 230-250°C (it decomposes above 250 according to wikipedia), to standardise permanganate titer solution against. They give no other recommended standard for manganometry, so I assume this is it.



I have no idea why anybody would want to use (or recommend using) the free acid instead, except perhaps to insult his first-year students' intelligence. Can't imagine it's much cheaper, in analytical grade.



For NaOH titer solution, Jander recommends using a secondary standard, e.g. HCl solution. HCl itself is standardised against freshly precipitated and dried sodium carbonate, or HgO ($ce+ 4 KI + H2O -> K2[HgI4] + 2 KOH$) dried over conc. sulfuric acid.






share|improve this answer











$endgroup$



Jander-Blasius (14. Ed., 1995) uses nonhygroscopic sodium oxalate, dried at 230-250°C (it decomposes above 250 according to wikipedia), to standardise permanganate titer solution against. They give no other recommended standard for manganometry, so I assume this is it.



I have no idea why anybody would want to use (or recommend using) the free acid instead, except perhaps to insult his first-year students' intelligence. Can't imagine it's much cheaper, in analytical grade.



For NaOH titer solution, Jander recommends using a secondary standard, e.g. HCl solution. HCl itself is standardised against freshly precipitated and dried sodium carbonate, or HgO ($ce+ 4 KI + H2O -> K2[HgI4] + 2 KOH$) dried over conc. sulfuric acid.







share|improve this answer














share|improve this answer



share|improve this answer








edited 12 hours ago

























answered yesterday









KarlKarl

6,1971434




6,1971434











  • $begingroup$
    Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
    $endgroup$
    – MaxW
    yesterday











  • $begingroup$
    I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
    $endgroup$
    – Karl
    yesterday










  • $begingroup$
    My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
    $endgroup$
    – MaxW
    13 hours ago










  • $begingroup$
    Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
    $endgroup$
    – Karl
    12 hours ago
















  • $begingroup$
    Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
    $endgroup$
    – MaxW
    yesterday











  • $begingroup$
    I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
    $endgroup$
    – Karl
    yesterday










  • $begingroup$
    My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
    $endgroup$
    – MaxW
    13 hours ago










  • $begingroup$
    Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
    $endgroup$
    – Karl
    12 hours ago















$begingroup$
Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
$endgroup$
– MaxW
yesterday





$begingroup$
Thanks! I can certainly understand standardizing HCl using NaCO3. However I'd wonder about the accuracy/precision of using HCL as a secondary standard. Just using KHP to standardize the NaOH would seem to be a better technique. KHP would only need 1 titration instead of 2.
$endgroup$
– MaxW
yesterday













$begingroup$
I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
$endgroup$
– Karl
yesterday




$begingroup$
I assume it is (or was) regarded as the better alternative, compared to using any of the widely available solid free acids. The book is a bit old school, perhaps KHP sounded too fancy for them. ;-)
$endgroup$
– Karl
yesterday












$begingroup$
My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
$endgroup$
– MaxW
13 hours ago




$begingroup$
My wonder in part of this was about what purity of oxalic acid dihydrate would be good enough for say a high school lab. I'm guessing that a relative standard deviation of 1% would be fine. So analytical grade might be more than is needed.
$endgroup$
– MaxW
13 hours ago












$begingroup$
Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
$endgroup$
– Karl
12 hours ago




$begingroup$
Our local supplier sells it at 20€/kg (>99%), 50€/kg for p.a. grade (>99.5%). KHP p.a. goes for 80 per kg. There are definitely simpler ways to ruin you high school chemistry budget. ;-)
$endgroup$
– Karl
12 hours ago

















draft saved

draft discarded
















































Thanks for contributing an answer to Chemistry Stack Exchange!


  • Please be sure to answer the question. Provide details and share your research!

But avoid


  • Asking for help, clarification, or responding to other answers.

  • Making statements based on opinion; back them up with references or personal experience.

Use MathJax to format equations. MathJax reference.


To learn more, see our tips on writing great answers.




draft saved


draft discarded














StackExchange.ready(
function ()
StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f111646%2fis-oxalic-acid-dihydrate-considered-a-primary-acid-standard-in-analytical-chemis%23new-answer', 'question_page');

);

Post as a guest















Required, but never shown





















































Required, but never shown














Required, but never shown












Required, but never shown







Required, but never shown

































Required, but never shown














Required, but never shown












Required, but never shown







Required, but never shown







Popular posts from this blog

រឿង រ៉ូមេអូ និង ហ្ស៊ុយលីយេ សង្ខេបរឿង តួអង្គ បញ្ជីណែនាំ

QGIS export composer to PDF scale the map [closed] Planned maintenance scheduled April 23, 2019 at 23:30 UTC (7:30pm US/Eastern) Announcing the arrival of Valued Associate #679: Cesar Manara Unicorn Meta Zoo #1: Why another podcast?Print Composer QGIS 2.6, how to export image?QGIS 2.8.1 print composer won't export all OpenCycleMap base layer tilesSave Print/Map QGIS composer view as PNG/PDF using Python (without changing anything in visible layout)?Export QGIS Print Composer PDF with searchable text labelsQGIS Print Composer does not change from landscape to portrait orientation?How can I avoid map size and scale changes in print composer?Fuzzy PDF export in QGIS running on macSierra OSExport the legend into its 100% size using Print ComposerScale-dependent rendering in QGIS PDF output

PDF-ში გადმოწერა სანავიგაციო მენიუproject page