Core Chemistry 14 - 16

+ water

The commonest carbonate-acid reaction you will come across is that between calcium carbonate and dilute hydrochloric acid.

Calcium carbonate occurs naturally as chalk, limestone and marble. The photo shows the reaction with marble chips.

You get immediate fizzing with a colourless gas given off - that's carbon dioxide. The marble reacts to give a colourless solution of calcium chloride.

CaCO (s) + 2HCl(aq)  (aq) + CO (g) + H O(l)

The reaction with dilute sulfuric acid is slightly more complicated because the calcium sulfate formed is only very slightly soluble.

The reaction starts, but almost immediately stops again because the marble chips get coated with a layer of calcium sulfate which prevents any more acid getting at the marble chip.

The photo shows what the reaction looks like a short time after you have added the acid. Nothing is happening.

All carbonates react in the same sort of way and that is because the same underlying bit of chemistry happens in each case.

Carbonate ions from the carbonate react with hydrogen ions from the acid.

CO (s or aq) + 2H (aq)  (g) + H O(l)

The "(s or aq)" is because a few carbonates (sodium, potassium and ammonium carbonates) are soluble in water, and so you might use a solution of one of these.

So if you added dilute hydrochloric acid to sodium carbonate solution, you would again get carbon dioxide produced - but this time everything would be in solution.

So what happens to the other ions? They are spectator ions.

In the hydrochloric acid / calcium carbonate case, the chloride ions are there in solution all the time. The calcium ions were originally present in the solid and end up in the solution, but they are still calcium ions.

So the solution contains calcium ions and chloride ions - calcium chloride solution.

Copper(II) carbonate is an insoluble green powder. This photo comes from .


The next video shows its reaction with dilute sulfuric and, and shows how you can test for the carbon dioxide given off.

CuCO (s) + H SO (aq)  (aq) + CO (g) + H O(l)

The ionic equation, showing the reaction between the carbonate and hydrogen ions, is exactly the same as before - except, of course, that we know copper(II) carbonate is a solid.

CO (s) + 2H (aq)  (g) + H O(l)

This time the spectator ions you are left with are copper(II) ions and sulfate ions in solution - blue copper(II) sulfate solution.

You test for carbon dioxide using lime water - a very dilute solution of calcium hydroxide in water. Lime water is a colourless solution and turns cloudy ("milky") when carbon dioxide is passed through it.

The calcium hydroxide reacts with the carbon dioxide to give insoluble calcium carbonate - that's what causes the cloudiness.

Ca(OH) (aq) + CO (g)   (s) + H O(l)

If you pass carbon dioxide through lime water for a long time, it first goes milky because of the formation of a precipitate of calcium carbonate, but then the precipitate disappears again giving a colourless solution.

The next bit of video shows this happening. The video is a bit clumsy but is chemically accurate.

) . Calcium hydrogencarbonate is soluble in water.

CaCO (s) + CO (g) + H O(l)   ) (aq)

This is the same reaction which produces cave systems in limestone rocks. Limestone is a form of calcium carbonate. Carbon dioxide dissolved in rain water gradually dissolves the rock over very long periods of time.

You will find compounds like sodium hydrogencarbonate also called "sodium hydrogen carbonate" (separate words) or the old name "sodium bicarbonate". I prefer the name "sodium hydrogencarbonate" because it shows that the hydrogen and carbonate are both part of the same HCO ion.

There are very few solid hydrogencarbonates - the only ones you are likely to meet are sodium and potassium hydrogencarbonates.

Calcium hydrogencarbonate only exists in solution. If you try to turn it into a solid, it splits up again into calcium carbonate and carbon dioxide and water.

Hydrogencarbonates react with acids in the same way as carbonates.

So, for example, if you add dilute hydrochloric acid to solid sodium hydrogencarbonate, it will react giving off colourless carbon dioxide gas and producing colourless sodium chloride solution.

NaHCO (s) + HCl(aq)  (g) + H O(l)

The ionic equation for the reaction is

HCO (s) + H (aq)  (g) + H O(l)

To be honest, at this level you might come across calcium hydrogencarbonate being formed in the lime water reaction, and you might come across sodium hydrogencarbonate being used to test for an acid. If you add solid sodium hydrogencarbonate to a liquid and get carbon dioxide given off, then the liquid must be acidic.

You might also come across calcium or magnesium hydrogencarbonates if you do a topic about hard water.

And that is about all you will need to know!

Rate of Reaction - Calcium Carbonate & Hydrochloric Acid ( OCR A Level Chemistry )

Revision note.

Richard

PAG 9.2: Rate of Reaction - Calcium Carbonate & Hydrochloric Acid

The reaction of calcium carbonate and hydrochloric acid.

  • Large chips
  • Small chips
  • The reaction itself cannot change

CaCO 3 (s) + 2HCl (aq) → CaCl 2 (aq) + H 2 O (l) + CO 2 (g)

  • However, the application and analysis of the results shifts more towards the mathematical skills of accurately plotting graphs, drawing tangents and calculating gradients
  • The volume of carbon dioxide gas produced
  • The mass loss from the reaction vessel

Method 1 - Volume of CO 2 produced

  • Support a gas syringe with a stand, boss and clamp.
  • Add 50 cm 3   of dilute hydrochloric acid to a conical flask
  • Loosely connect the gas syringe 
  • Measure 0.40 g of calcium carbonate
  • Add the 0.40 g of calcium carbonate into the conical flask, replace the gas syringe and start the stopwatch
  • Record the volume of gas produced every 10 seconds. Continue timing until no more carbon dioxide appears to be given off
  • This method still records the volume of carbon dioxide produced

Specimen results 1 - Volume of CO 2 produced

  • Here is a set of typical results for this experiment

Rate of carbon dioxide production in the reaction of calcium carbonate and hydrochloric acid table

10 20 30 40 50 60
produced (cm ) 34 57 69 71 72 72

Graphing the results 1 - Volume of CO 2 produced

1-4-2-caco3-and-hcl-reaction-rate-graph-1

Analysis 1 - Volume of CO 2 produced

  • The curve of best fit is drawn on the graph
  • A tangent can then drawn starting from (0,0) to find the   initial rate   of reaction
  • This is the rate of reaction

1-4-2-caco3-and-hcl-reaction-rate-graph-2

Method 2 - Mass of the reaction vessel

  • Measure 0.40 g of calcium carbonate into a weighing boat
  • Add 50 cm 3  of dilute hydrochloric acid to a conical flask
  • Place the conical flask of hydrochloric acid AND the weighing boat of calcium carbonate onto the balance
  • Measure the combined mass and record this as the  t = 0 result
  • Add the 0.40 g of calcium carbonate into the conical flask, replace the weighing boat onto the balance and start the stopwatch
  • Record the mass every 10 seconds. Continue timing until no further mass is lost
  • It may be necessary to use more dilute concentrations of hydrochloric acid because it may not be realistically possible to record the mass every second
  • A data logger could be connected to the balance (if available) and this can track the mass over time 

Specimen results 2 - Mass of the reaction vessel

Rate of change in mass in the reaction of calcium carbonate and hydrochloric acid table

0 10 20 30 40 50 60
302.700 302.650 302.600 302.580 302.568 302.568 302.568

Graphing the results 2 - Mass of the reaction vessel

1-4-2-caco3-and-hcl-mass-reaction-rate-graph-1

Analysis 2 - Mass of the reaction vessel

1-4-2-caco3-and-hcl-mass-reaction-rate-graph-2

  • This then records the mass lost and can be used to give a graph with a curve more like the volume of CO 2 produced graph

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  • Further Physical Chemistry Practicals
  • Atoms & Reactions
  • Amount of Substance
  • Acid-base & Redox Reactions
  • Electrons, Bonding & Structure
  • The Shapes of Simple Molecules & Ions
  • Periodicity
  • The Halogens
  • Enthalpy Changes

Author: Richard

Richard has taught Chemistry for over 15 years as well as working as a science tutor, examiner, content creator and author. He wasn’t the greatest at exams and only discovered how to revise in his final year at university. That knowledge made him want to help students learn how to revise, challenge them to think about what they actually know and hopefully succeed; so here he is, happily, at SME.

3:15 practical: investigate the effect of changing the surface area of marble chips and of changing the concentration of hydrochloric acid on the rate of reaction between marble chips and dilute hydrochloric acid

The rate of a chemical reaction can be measured either by how quickly reactants are used up or how quickly the products are formed.

The rate of reaction can be calculated using the following equation:

calcium carbonate and nitric acid experiment

The units for rate of reaction will usually be grams per min (g/min)

An investigation of the reaction between marble chips and hydrochloric acid:

calcium carbonate and nitric acid experiment

Using the apparatus shown the change in mass of carbon dioxide can be measure with time.

As the marble chips react with the acid, carbon dioxide is given off.

The purpose of the cotton wool is to allow carbon dioxide to escape, but to stop any acid from spraying out.

The mass of carbon dioxide lost is measured at intervals, and a graph is plotted:

calcium carbonate and nitric acid experiment

Experiment to investigate the effects of changes in surface area of solid on the rate of a reaction:

The experiment is repeated using the exact same quantities of everything but using larger chips. For a given quantity, if the chips are larger then the surface area is lesson. So reaction with the larger chips happens more slowly.

Both sets of results are plotted on the same graph.

calcium carbonate and nitric acid experiment

Experiment to investigate the effects of changes in concentration of solutions on the rate of a reaction:

The experiment is again repeated using the exact same quantities of everything but this time with half the concentration of acid. The marble chips must however be in excess. The reaction with the half the concentration of acid happens slower and produces half the amount of carbon dioxide.

calcium carbonate and nitric acid experiment

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PMMA (Polymethyl Methacrylate) – Chemical Resistance Chart

PMMA (Polymethyl Methacrylate) – Chemical Resistance Chart

When selecting chips for microfluidic applications, ensuring chemical resistance is crucial for maintaining system integrity and performance. PMMA (Polymethyl Methacrylate) is a popular choice due to its optically clear nature, lightweight properties, and shatter-resistant characteristics. It is commonly used in medical, pharmaceutical, and food processing applications because of its excellent resistance to water, alcohols, and a variety of chemicals.

However, like all materials, PMMA has its limitations, and not every chemical is compatible with it. Therefore, understanding resistance is essential for preventing chip degradation and ensuring safety. In this guide, we present a comprehensive table of chemical resistance for PMMA chips. This table, based on the chemical resistance data (at 20°C) provided by Reichelt Chemietechnik , is designed to help engineers, technicians, and researchers quickly determine whether PMMA chips are suitable for their specific applications, ensuring reliable and long-lasting performance in various chemical environments.

Refer to this table to make informed choices and maintain the efficiency and safety of your system.

💡 The chemical resistance rating key is as follows:

  • resistant = no effect to slight effect
  • limited resistance = moderate effect 

🚨 The resistance ratings provided in these tables are for general guidance only and may not be complete or accurate. They do not address potential contamination or changes in fluid properties due to tubing interaction. We do not guarantee the suitability of any material for specific purposes or the impact of tubing on fluid quality. For critical applications, conduct specific tests or seek expert advice.

PMMA Chips: Chemical Resistance Table

Substance/MediaChemical Resistance
A
Acetyl cellulose (cellulose acetate)resistant
Adipic acidresistant
Aluminum chlorideresistant
Aluminum hydroxidelimited resistance
Aluminum nitrateresistant
Aluminum sulfateresistant
Amino acidsresistant
Ammonia solutionresistant
Ammonia, aqueous (ammonia solution)resistant
Ammonium carbonate (sal volatile)resistant
Ammonium chloride (salmiac)limited resistance
Ammonium fluoride (Fluorammon)limited resistance
Ammonium hydroxide, 30%resistant
Ammonium hydroxide, aqueousresistant
Ammonium nitrate (fertilizer)resistant
Ammonium phosphate (fertilizer)resistant
Ammonium salts of mineral acidsresistant
Ammonium sulfate (fertilizer)resistant
Antichlor (sodium thiosulfate, fixing salt)resistant
Argon gasresistant
B
Barium chlorideresistant
Barium salts of mineral acidsresistant
Beerresistant
Blue vitriol (copper sulfate)resistant
Borax (sodium tetraborate)resistant
Boric acidresistant
Boric acid, 10%resistant
Butanol-1 (butyl alcohol)limited resistance
C
Calcium carbonate (chalk)resistant
Calcium chlorideresistant
Calcium chloride, aqueousresistant
Calcium hydroxide (milk of lime)resistant
Calcium hypochloritelimited resistance
Calcium hypochlorite, aqueousresistant
Calcium sulfate (gypsum)resistant
Caliche solution (Chile saltpeter)resistant
Carbon tetrachloride (tetrachloromethane)limited resistance
Carbon tetrachloride (tetrachloromethane, tetra)limited resistance
Carbonic acidresistant
Caustic potash (potassium hydroxide, potash lye)resistant
Caustic soda (sodium hydroxide)resistant
Caustic soda (sodium hydroxide, soda lye)resistant
Cellulose acetate (acetyl cellulose)resistant
Chalk (calcium carbonate)resistant
Chloroacetic acid (ethyl chloroacetate)limited resistance
Chloroacetic acid ethyl ester (ethyl chloroacetate)limited resistance
Chromic acid, 10%limited resistance
Chromic acid, 50%limited resistance
Chromium anhydride (chromium trioxide)limited resistance
Chromium trioxide (chromium anhydride)limited resistance
Citric acidlimited resistance
Citric acid, aqueouslimited resistance
Citrus fruits, citrus juicesresistant
Common salt (sodium chloride)resistant
Cooking fats, cooking oilsresistant
Copper sulfate (blue vitriol)resistant
Crude oilresistant
Cycloaliphatic hydrocarbonsresistant
Cyclohexanol (hexalin, anol)resistant
D
Decahydronaphthalene (decane)limited resistance
Decalin (decahydronaphthalene, decane)limited resistance
Dextrin, aqueousresistant
Dibutyl sebacatelimited resistance
Diesel fuelresistant
Diesel oillimited resistance
Dihydroxysuccinic acid (tartaric acid)limited resistance
E
Epsom salts (magnesium sulfate)resistant
Ethanedioic acid (oxalic acid), aqueousresistant
Ethyl chloroacetate (chloroacetic acid ethyl ester)limited resistance
Ethylene glycol (glycol, 1,2-ethanediol)resistant
Ethylene oxideresistant
F
Fats, cooking oilsresistant
Fatty acidsresistant
Ferric chloride (iron(III) chloride)limited resistance
Ferrous chloride (iron(II) chloride)resistant
Fixing salt (antichlor, sodium thiosulfate)resistant
Fluorammon (ammonium fluoride)limited resistance
Formaldehyde (formalin, methanal)resistant
Formamideresistant
Formic acidresistant
Freon (Frigen) 12resistant
Fruit juicesresistant
Fuel oil, mineral oil-basedlimited resistance
G
Gasolineresistant
Gasoline, premiumresistant
Gasoline, unleadedresistant
Glucose (grape sugar)resistant
Glycerine (glycerol)resistant
Glycol (ethylene glycol)resistant
Grape sugar (glucose)resistant
Gypsum (calcium sulfate)resistant
H
Heptanelimited resistance
Hexalin (cyclohexanol)resistant
Hexanelimited resistance
Hexanoic acidresistant
Hexanol (hexyl alcohol)resistant
Hexyl alcohol (hexanol)resistant
Hydrochloric acid (muriatic acid), 10%limited resistance
Hydrochloric acid (muriatic acid), 20%limited resistance
Hydrochloric acid (muriatic acid), 37%limited resistance
Hydrochloric acid (muriatic acid), concentratedlimited resistance
Hydrochloric acid (spirits of salt)limited resistance
Hydrofluorosilicic acid (silicic acid)resistant
Hydrogen peroxide, dilutedresistant
Hydrogen sulfideresistant
Hydrogen, gaseousresistant
I
Iron sulfate (iron vitriol), aqueousresistant
Iron(II) chloride, aqueous (ferrous chloride)resistant
Iron(III) chloride (ferric chloride)limited resistance
Isobutanol (isobutyl alcohol)limited resistance
Isobutyl alcohol (isobutanol)limited resistance
Isopropanol (2-propanol)limited resistance
Isopropyl alcohol (isopropanol, persprit)limited resistance
J
Javel water (sodium hypochlorite, bleaching solution)resistant
K
Keroseneresistant
L
Lactic acidlimited resistance
Lactic acid, concentratedlimited resistance
Lanolin (wool grease)resistant
M
Magnesium carbonateresistant
Magnesium chloride, aqueousresistant
Magnesium nitrateresistant
Magnesium sulfate (Epsom salt)resistant
Maltresistant
Manganese sulfate, aqueous, 10%resistant
Mercuryresistant
Mercury (II) chlorideresistant
Mercury chlorideresistant
Methanal (formaldehyde)resistant
Methane (mine gas, natural gas)resistant
Methylamine (monomethylamine)resistant
Milkresistant
Milk of lime (calcium hydroxide)resistant
Mine gas (methane, natural gas)resistant
Mineral oilsresistant
Monochloroacetic acidlimited resistance
Mortar, cement, limeresistant
N
n-amyl acetateresistant
Naphtharesistant
Natural gas (mine gas, methane)resistant
Nickel sulfateresistant
Nitric acid, 10%resistant
Nitric acid, 30%limited resistance
Nitric acid, 70%limited resistance
Nitrogenresistant
O
Octanelimited resistance
Oleic acidresistant
Oleum (fuming sulfuric acid)limited resistance
Oxalic acid (ethanedioic acid)resistant
Oxalic acid (ethanedioic acid), aqueousresistant
Oxygenresistant
Ozoneresistant
P
Paraffin (alkane)resistant
Perchloroethylene (tetrachloroethylene)limited resistance
Petroleumresistant
Petroleum etherresistant
Phosphoric acid, 10%resistant
Polyester resinsresistant
Potassium bichromatelimited resistance
Potassium carbonateresistant
Potassium carbonate (potash)resistant
Potassium chlorateresistant
Potassium chloride (sylvine)resistant
Potassium cyanideresistant
Potassium dichromatelimited resistance
Potassium hydroxide (caustic potash, potash lye)resistant
Potassium hypochloriteresistant
Potassium nitrate (saltpeter)resistant
Potassium permanganateresistant
Potassium permanganate, aqueousresistant
Propanol (propyl alcohol)limited resistance
Propyl alcohol (propanol)limited resistance
S
Sal ammoniac (ammonium chloride)limited resistance
Sal volatile (ammonium carbonate)resistant
Salt water (sea water)resistant
Saltpeter (potassium nitrate)resistant
Sea water (salt water)resistant
Silicic acid (hydrofluorosilicic acid)resistant
Silicone greaseresistant
Silicone oilresistant
Silver acetatelimited resistance
Silver nitrate (lunar caustic)resistant
Soda (sodium carbonate), aqueousresistant
Sodium acetateresistant
Sodium bicarbonate, aqueousresistant
Sodium bisulfate, aqueousresistant
Sodium bisulfite, aqueousresistant
Sodium borate, aqueousresistant
Sodium bromideresistant
Sodium carbonate (soda), aqueousresistant
Sodium chlorate, aqueousresistant
Sodium chloride (common salt)resistant
Sodium cyanideresistant
Sodium dichromateresistant
Sodium fluorideresistant
Sodium formate, aqueousresistant
Sodium hydroxide (caustic soda, soda lye)resistant
Sodium hypochlorite (bleaching solution, Javel water)resistant
Sodium hypochlorite (bleaching solution, Javel water), 12.5%resistant
Sodium hypochlorite (bleaching solution, Javel water), 15%resistant
Sodium hypochlorite (bleaching solution, Javel water), dilutedresistant
Sodium hypochlorite (bleaching solution, Javel water), saturatedresistant
Sodium iodideresistant
Sodium nitrate (Chile saltpeter)resistant
Sodium nitrite, aqueousresistant
Sodium phosphate, aqueousresistant
Sodium silicate, aqueousresistant
Sodium sulfate (Glauber's salt), aqueousresistant
Sodium sulfideresistant
Sodium sulfide, aqueousresistant
Sodium sulfiteresistant
Sodium tetraborate (borax)resistant
Sodium thiosulfate (antichlor, fixing salt)resistant
Stearic acid (zinc salt)resistant
Sulfurresistant
Sulfur dioxideresistant
Sulfuric acid, 10%resistant
Sulfuric acid, 60%limited resistance
Sulfuric acid, fuming (20/25% oleum)limited resistance
T
Tartaric acid (dihydroxysuccinic acid)limited resistance
Tetrachloroethylene (perchloroethylene)limited resistance
Tetrachloromethane (carbon tetrachloride)limited resistance
Tin (II) chlorideresistant
Triethylamine (TEA)resistant
Triethylene glycollimited resistance
Tripropylene glycol (TPG)limited resistance
Turpentineresistant
U
Urearesistant
Urea, aqueousresistant
V
Vinegarresistant
W
Water, with carbon dioxideresistant
Water/Spring water, coldresistant
Wool grease (lanolin)resistant
Z
Zinc salt (stearic acid)resistant
Zinc sulfatelimited resistance
Zinc sulfate, aqueousresistant

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calcium carbonate and nitric acid experiment

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Acid–base back titration

By Sandrine Bouchelkia and Jo Haywood

  • Five out of five

Experiment and develop learners’ quantitative analysis skills

This resource accompanies the article The essential guide to teaching quantitative chemistry in  Education in Chemistry , where you will find tips, common misconceptions and further ideas for teaching reacting masses and limiting reagents. 

Use the technician notes to prepare the practical and find the experimental procedure in the student worksheet.

Preview of Acid–base back titration calculation slides, spreadsheet, student worksheet, teacher and technician notes

Download this

Use the experiment and accompanying resources, including answers, to develop your post-16 learners' quantitative chemistry skills.

Learning objectives

  • Apply your knowledge of mole calculations to practical experimental data.
  • Write balanced equations for practical experiments.
  • Review practical techniques.

Learners will address all three objectives throughout the experiment. They should successfully carry out the practical, write relevant balanced equations and utilise these to carry out mole calculations. Learners will draw their findings together in a conclusion and evaluation, comparing their experimental and theoretical data. Find the answers in the teacher notes and use the accompanying mole calculator spreadsheet to check learners’ calculations.

Scaffolding

Some learners will be keen to work through the whole task independently. Others will benefit from you checking the calculation steps as they go along, ensuring they have correctly balanced the equations and found the masses and moles before they write their conclusion and evaluation. Use the PowerPoint  (also available as a  pdf ) to model each step of the calculation. Remove the example tables in the student sheet to encourage learners to draw their own or leave them in for support.

As an extension, ask learners to titrate the original HCl against the NaOH to check the concentration is correct. They can also investigate the effect of CO 2 dissolving on the pH of water .

Safety and hazards

  • Read our standard health and safety guidance  and carry out a risk assessment before running any live practical.
  • Eye protection must be worn.
  • The flask containing hydrochloric acid and calcium carbonate may get warm.
  • Instruct learners to take care not to spill solutions, particularly phenolphthalein, on their skin. If they do get any on their skin, rinse well.
  • Fill the burette at eye level.

Do the experiment individually or as a pair/small group. Each learner/group will require:

  • Two 100 ml conical flasks
  • 25 ml or 50 ml pipette
  • 10 ml pipette
  • Pipette fillers sized to match pipettes
  • Mass balance measuring three decimal places (0.001 g)*
  • Clamp and retort
  • Cotton wool
  • Safety equipment: safety glasses

*If a mass balance measuring three decimal places is not available then use a mass balance measuring two decimal places (0.01 g). This will be less accurate though.

  • Hydrochloric acid, 1.00 mol dm -3
  • Calcium carbonate chips (approx 1.00 g)
  • Sodium hydroxide, 0.400 mol dm -3
  • Phenolphthalein indicator solution in dropper bottles

More resources

  • Develop learners’ practical skills by ensuring your feedback is meaningful with the  Common Practical Assessment Criteria (CPAC) tracker .
  • Use the  Quantitative chemistry starters to practice skills relating to concentration, mass and gas calculations with your 16–18 learners. 
  • Bring together organic chemistry and moles calculations with the  Aspirin screen experiment .
  • Review your 14–16 year-old learners’ understanding of key ideas, words and phrases relating to quantitative chemistry by downloading the  scaffolded, partially scaffolded and unscaffolded worksheets .
  • Solidify you knowledge with the  Quantitative chemistry online CPD course  and download the accompanying resources  too.
  • Prepare tables for your results before you start your experiments.
  • Using the pipette, accurately measure out 50 ml of 1.00 mol dm -3 hydrochloric acid and add this to the conical flask. Place a piece of cotton wool in the top of the flask.
  • Measure the mass of the flask, cotton wool and hydrochloric acid. Record this in the table.
  • Using the three decimal places (dp) mass balance, accurately weigh out between 1.000 and 1.500 g (1.00 to 1.50 g for the two dp mass balance) of calcium carbonate and record the mass in the table.
  • Add the calcium carbonate to the hydrochloric acid and swirl the flask until all of the calcium carbonate has reacted.
  • Measure the final mass of the flask and contents and record in the table.
  • Fill the burette with sodium hydroxide solution (0.400 mol dm -3 ) using a funnel and pouring at your eye level.
  • Using a 10 ml pipette, measure out 10 ml of your reaction mixture into a clean 100 ml conical flask.
  • Add a few drops of phenolphthalein to the flask containing your reaction mixture. The mixture should remain colourless.
  • Titrate your mixture with the sodium hydroxide from your burette, recording how much sodium hydroxide you require to turn the mixture pink.
  • Rinse the conical titration flask with distilled water.
  • Repeat steps 6–11 until you have two results, excluding the rough titration, which are within 0.05 ml of each other (or you run out of reaction mixture).
  • Calculate the average titre to use in the calculations.

Acid–base back titration student sheet

Acid–base back titration teacher notes, acid–base back titration technician notes, acid–base back titration calculation slides, acid–base back titration mole calculator, additional information.

Resource created by Jo Haywood. Technician notes adapted by Sandrine Bouchelkia.

  • 16-18 years
  • Practical experiments
  • Presentation
  • Teacher notes
  • Technician notes
  • Maths skills
  • Practical skills and safety
  • Investigation
  • Applying scientific method
  • Acids and bases
  • Quantitative chemistry and stoichiometry
  • Asking scientific questions
  • Observing and measuring
  • Recording data
  • Interpreting data
  • Reactions and synthesis

Specification

  • C5.1b describe the technique of titration
  • Students should be able to: describe how to carry out titrations using strong acids and strong alkalis only (sulfuric, hydrochloric and nitric acids only) to find the reacting volumes accurately
  • (HT) Calculate the chemical quantities in titrations involving concentrations in mol/dm³ and in g/dm³.
  • C5.4.7 describe and explain the procedure for a titration to give precise, accurate, valid and repeatable results
  • C5.3.6 describe and explain the procedure for a titration to give precise, accurate, valid and repeatable results
  • AT f: Use acid–base indicators in titrations of weak/strong acids with weak/strong alkalis.
  • Titrations of acids with bases.
  • Students should be able to perform calculations for these titrations based on experimental results.
  • 11. be able to calculate solution concentrations, in mol dm⁻³ and g dm⁻³, including simple acid-base titrations using a range of acids, alkalis and indicators. The use of both phenolphthalein and methyl orange as indicators will be expected.
  • 4. use laboratory apparatus for a variety of experimental techniques, including:
  • titration, using burette and pipette
  • 6. use acid-base indicators in titrations of weak/strong acids with weak/strong alkalis
  • di) use of laboratory apparatus for a variety of experimental techniques including: i) titration, using burette and pipette
  • f) use of acid–base indicators in titrations of weak/ strong acids with weak/strong alkalis
  • d) the techniques and procedures used when preparing a standard solution of required concentration and carrying out acid–base titrations
  • carrying out a back titration
  • quantitative stoichiometric calculations
  • Back titration is used to find the number of moles of a substance by reacting it with an excess volume of reactant of known concentration.
  • The resulting mixture is then titrated to work out the number of moles of the reactant in excess.
  • From the initial number of moles of that reactant the number of moles used in the reaction can be determined, making it possible to work back to calculate the initial number of moles of the substance under test.
  • A back titration is useful when trying to work out the quantity of substance in a solid with a low solubility.
  • Stoichiometry is the study of quantitative relationships involved in chemical reactions.
  • The ability to balance and interpret equations enabling calculations to be carried out involving any of the above skills/techniques is an important part of chemistry at this level and is examinable in both the Unit and Course assessments.
  • process and analyse data using appropriate mathematical skills as exemplified in the mathematical appendix for each science
  • consider margins of error, accuracy and precision of data
  • follow written instructions
  • make and record observations
  • keep appropriate records of experimental activities
  • present information and data in a scientific way
  • evaluate results and draw conclusions with reference to measurement uncertainties and errors
  • comment on experimental design and evaluate scientific methods
  • use laboratory apparatus for a variety of experimental techniques including: titration, using burette and pipette
  • use acid-base indicators in titrations of weak/strong acids with weak/strong alkalis
  • carry out experimental and investigative activities, including appropriate risk management, in a range of contexts
  • evaluate methodology, evidence and data, and resolve conflicting evidence
  • (f) acid-base titrations
  • PRACTICAL: Back titration, for example, determination of the percentage of calcium carbonate in limestone
  • (f) relationship between grams and moles
  • (g) concept of concentration and its expression in terms of grams or moles per unit volume (including solubility)
  • (j) concept of stoichiometry and its use in calculating reacting quantities, including in acid-base titrations
  • 5.3.4 demonstrate understanding of the method of back titration, for example by determining the purity of a Group II metal oxide or carbonate.
  • determine the purity of a Group II metal oxide or carbonate by back titration;
  • use volumetric flasks to prepare standard solutions of various volumes and safely use a burette and a pipette with acid-base indicators to carry out titrations of weak or strong acids with weak or strong alkalis;
  • Calculations involving excess of one reactant.
  • Apparatus used in volumetric analysis.
  • Correct titrimetric procedure.
  • Acid-base titrations.

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The facile production of p -chloroaniline facilitated by an efficient and chemoselective metal-free n/s co-doped carbon catalyst.

calcium carbonate and nitric acid experiment

1. Introduction

3. discussion, 4. materials and methods, 4.1. materials synthesis, 4.2. material characterization, 4.3. catalytic tests, 5. conclusions, supplementary materials, author contributions, institutional review board statement, informed consent statement, data availability statement, conflicts of interest.

  • Könnecker, G.; Boehncke, A.; Schmidt, S. Ecotoxicological assessment of p-chloroaniline—Fate and effects in aquatic systems. Fresenius Environ. Bull. 2003 , 12 , 589–593. [ Google Scholar ]
  • Dighe, S.U.; Juliá, F.; Luridiana, A.; Douglas, J.J.; Leonori, D. A photochemical dehydrogenative strategy for aniline synthesis. Nature 2020 , 584 , 75–81. [ Google Scholar ] [ CrossRef ]
  • Raghav, A. Aniline Market Report 2022–2027, Size, Share, Growth, Price Trends and Forecast ; IndustryARC: Hyderabad, India, 2022. [ Google Scholar ]
  • Qiu, Z.; Lv, L.; Li, J.; Li, C.-C.; Li, C.-J. Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium. Chem. Sci. 2019 , 10 , 4775–4781. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Schmidt, V.A. Game-changing recipe for chemical building blocks. Nature 2020 , 584 , 46–47. [ Google Scholar ] [ CrossRef ]
  • Kadam, H.K.; Tilve, S.G. Advancement in methodologies for reduction of nitroarenes. RSC Adv. 2015 , 5 , 83391–83407. [ Google Scholar ] [ CrossRef ]
  • Tokiwa, H.; Nakagawa, R.; Horikawa, K.; Ohkubo, A. The nature of the mutagenicity and carcinogenicity of nitrated, aromatic compounds in the environment. Environ. Heal. Perspect. 1987 , 73 , 191–199. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Kuppusamy, A.J.; Senthilkumar Perumal, W. Toxicity Values for p-Chloronitrobenzene (CASRN 100-00-5) ; EPA/690/R-15/004F Final 9-30-2015; United States Environmental Protection Agency, USEPA: Washington, DC, USA, 2015; pp. 1–9.
  • Béchamp, A. De l’action des protosels de fer sur la nitronaphtaline et la nitrobenzine: Nouvelle méthode de formation des bases orgnaiques artificielles de zinin. Ann. Chim. Phys. 1854 , 42 , 186. [ Google Scholar ]
  • Serna, P.; Corma, A. Transforming Nano Metal Nonselective Particulates into Chemoselective Catalysts for Hydrogenation of Substituted Nitrobenzenes. ACS Catal. 2015 , 5 , 7114–7121. [ Google Scholar ] [ CrossRef ]
  • Jakab-Nácsa, A.; Sikora, E.; Prekob, Á.; Vanyorek, L.; Szőri, M.; Boros, R.Z.; Nehéz, K.; Szabó, M.; Farkas, L.; Viskolcz, B. Comparison of Catalysts with MIRA21 Model in Heterogeneous Catalytic Hydrogenation of Aromatic Nitro Compounds. Catalysts 2022 , 12 , 467. [ Google Scholar ] [ CrossRef ]
  • Cárdenas-Lizana, F.; Gómez-Quero, S.; Perret, N.; Kiwi-Minsker, L.; Keane, M.A. β-Molybdenum nitride: Synthesis mechanism and catalytic response in the gas phase hydrogenation of p-chloronitrobenzene. Catal. Sci. Technol. 2011 , 1 , 794–801. [ Google Scholar ] [ CrossRef ]
  • Turáková, M.; Salmi, T.; Eränen, K.; Wärnå, J.; Murzin, D.Y.; Králik, M. Liquid phase hydrogenation of nitrobenzene. Appl. Catal. A Gen. 2015 , 499 , 66–76. [ Google Scholar ] [ CrossRef ]
  • Sahoo, B.; Formenti, D.; Topf, C.; Bachmann, S.; Scalone, M.; Junge, K.; Beller, M. Biomass-Derived Catalysts for Selective Hydrogenation of Nitroarenes. ChemSusChem 2017 , 10 , 3035–3039. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Sheng, Y.; Wu, B.; Ren, J.; Wang, X.; Zou, X.; Lu, X. Efficient and recyclable bimetallic Co–Cu catalysts for selective hydrogenation of halogenated nitroarenes. J. Alloy. Compd. 2022 , 897 , 163143. [ Google Scholar ] [ CrossRef ]
  • Formenti, D.; Ferretti, F.; Scharnagl, F.K.; Beller, M. Reduction of Nitro Compounds Using 3d-Non-Noble Metal Catalysts. Chem. Rev. 2018 , 119 , 2611–2680. [ Google Scholar ] [ CrossRef ]
  • Campos, C.H.; Shanmugaraj, K.; Bustamante, T.M.; Leal-Villarroel, E.; Vinoth, V.; Aepuru, R.; Mangalaraja, R.V.; Torres, C.C. Catalytic production of anilines by nitro-compounds hydrogenation over highly recyclable platinum nanoparticles supported on halloysite nanotubes. Catal. Today 2021 , 394–396 , 510–523. [ Google Scholar ] [ CrossRef ]
  • Romanazzi, G.; Fiore, A.M.; Mali, M.; Rizzuti, A.; Leonelli, C.; Nacci, A.; Mastrorilli, P.; Dell’anna, M.M. Polymer supported Nickel nanoparticles as recyclable catalyst for the reduction of nitroarenes to anilines in aqueous medium. Mol. Catal. 2018 , 446 , 31–38. [ Google Scholar ] [ CrossRef ]
  • Petrelli, V.; Romanazzi, G.; Mortalò, C.; Leonelli, C.; Zapparoli, M.; De Giglio, E.; Calvano, C.D.; Dell’Anna, M.M.; Mastrorilli, P. N-doped resin supported cobalt nanoparticles for the catalytic reduction of nitroarenes to corresponding anilines in aqueous medium. Mol. Catal. 2023 , 544 , 11305. [ Google Scholar ] [ CrossRef ]
  • Fiore, A.M.; Varvaro, G.; Agostinelli, E.; Mangone, A.; De Giglio, E.; Terzano, R.; Allegretta, I.; Dell’Anna, M.M.; Fiore, S.; Mastrorilli, P. Synthesis and Use in Catalysis of Hematite Nanoparticles Obtained from a Polymer Supported Fe(III) Complex. Eur. J. Inorg. Chem. 2022 , 2022 , e202100943. [ Google Scholar ] [ CrossRef ]
  • Cárdenas-Lizana, F.; Hao, Y.; Crespo-Quesada, M.; Yuranov, I.; Wang, X.; Keane, M.A.; Kiwi-Minsker, L. Selective Gas Phase Hydrogenation of p -Chloronitrobenzene over Pd Catalysts: Role of the Support. ACS Catal. 2013 , 3 , 1386–1396. [ Google Scholar ] [ CrossRef ]
  • Prekob, Á.; Szamosvölgyi, Á.; Muránszky, G.; Lakatos, J.; Kónya, Z.; Fiser, B.; Viskolcz, B.; Vanyorek, L. Palladium Decorated N -Doped Carbon Foam as a Highly Active and Selective Catalyst for Nitrobenzene Hydrogenation. Int. J. Mol. Sci. 2022 , 23 , 6423. [ Google Scholar ] [ CrossRef ]
  • Cárdenas-Lizana, F.; Gómez-Quero, S.; Keane, M.A. Ultra-selective gas phase catalytic hydrogenation of aromatic nitro compounds over Au/Al2O3. Catal. Commun. 2008 , 9 , 475–481. [ Google Scholar ] [ CrossRef ]
  • Yue, S.; Wang, X.; Li, S.; Sheng, Y.; Zou, X.; Lu, X.; Zhang, C. Highly selective hydrogenation of halogenated nitroarenes over Ru/CN nanocomposites by in situ pyrolysis. New J. Chem. 2020 , 44 , 11861–11869. [ Google Scholar ] [ CrossRef ]
  • Dongil, A.; Rivera-Cárcamo, C.; Pastor-Pérez, L.; Sepúlveda-Escribano, A.; Reyes, P. Ir supported over carbon materials for the selective hydrogenation of chloronitrobenzenes. Catal. Today 2015 , 249 , 72–78. [ Google Scholar ] [ CrossRef ]
  • Hu, Z.-N.; Liang, J.; Ding, K.; Ai, Y.; Liang, Q.; Sun, H.-B. Insight into the selectivity of nano-catalytic nitroarenes reduction over other active groups by exploring hydrogen sources and metal components. Appl. Catal. A Gen. 2021 , 626 , 118339. [ Google Scholar ] [ CrossRef ]
  • Cheong, W.-C.; Yang, W.; Zhang, J.; Li, Y.; Zhao, D.; Liu, S.; Wu, K.; Liu, Q.; Zhang, C.; Wang, D.; et al. Isolated Iron Single-Atomic Site-Catalyzed Chemoselective Transfer Hydrogenation of Nitroarenes to Arylamines. ACS Appl. Mater. Interfaces 2019 , 11 , 33819–33824. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Villora-Picó, J.J.; Campello-Gómez, I.; Serrano-Ruiz, J.C.; Pastor-Blas, M.M.; Sepúlveda-Escribano, A.; Ramos-Fernández, E.V. Hydrogenation of 4-nitrochlorobenzene catalysed by cobalt nanoparticles supported on nitrogen-doped activated carbon. Catal. Sci. Technol. 2021 , 11 , 3845–3854. [ Google Scholar ] [ CrossRef ]
  • Duran-Uribe, E.S.; Sepúlveda-Escribano, A.; Ramos-Fernandez, E.V. Microwave-assisted synthesis of CoxP@C catalysts: Application to the hydrogenation of 1-chloro-4-nitrobezene. Chem. Eng. J. 2023 , 474 , 145897. [ Google Scholar ] [ CrossRef ]
  • Cárdenas-Lizana, F.; Gómez-Quero, S.; Keane, M.A. Clean production of chloroanilines by selective gas phase hydrogenation over supported Ni catalysts. Appl. Catal. A Gen. 2008 , 334 , 199–206. [ Google Scholar ] [ CrossRef ]
  • Pothu, R.; Challa, P.; Rajesh, R.; Boddula, R.; Balaga, R.; Balla, P.; Perugopu, V.; Radwan, A.B.; Abdullah, A.M.; Al-Qahtani, N. Vapour-Phase Selective Hydrogenation of γ-Valerolactone to 2-Methyltetrahydrofuran Biofuel over Silica-Supported Copper Catalysts. Nanomaterials 2022 , 12 , 3414. [ Google Scholar ] [ CrossRef ]
  • Xiong, W.; Wang, Z.; He, S.; Hao, F.; Yang, Y.; Lv, Y.; Zhang, W.; Liu, P.; Luo, H. Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for nitrobenzene hydrogenation. Appl. Catal. B Environ. 2019 , 260 , 118105. [ Google Scholar ] [ CrossRef ]
  • Lara, P.; Philippot, K. The hydrogenation of nitroarenes mediated by platinum nanoparticles: An overview. Catal. Sci. Technol. 2014 , 4 , 2445–2465. [ Google Scholar ] [ CrossRef ]
  • Gao, R.; Pan, L.; Lu, J.; Xu, J.; Zhang, X.; Wang, L.; Zou, J. Phosphorus-Doped and Lattice-Defective Carbon as Metal-like Catalyst for the Selective Hydrogenation of Nitroarenes. ChemCatChem 2017 , 9 , 4287–4294. [ Google Scholar ] [ CrossRef ]
  • Song, J.; Huang, Z.-F.; Pan, L.; Li, K.; Zhang, X.; Wang, L.; Zou, J.-J. Review on selective hydrogenation of nitroarene by catalytic, photocatalytic and electrocatalytic reactions. Appl. Catal. B Environ. 2018 , 227 , 386–408. [ Google Scholar ] [ CrossRef ]
  • Dasgupta, H.R.; Mukherjee, S.; Ghosh, P. A novel approach towards chemoselective reduction of nitro to amine. Tetrahedron Lett. 2019 , 60 , 151028. [ Google Scholar ] [ CrossRef ]
  • Mayoral, E.P.; Ojer, M.G.; Ventura, M.; Matos, I. New Insights into N -Doped Porous Carbons as Both Heterogeneous Catalysts and Catalyst Supports: Opportunities for the Catalytic Synthesis of Valuable Compounds. Nanomaterials 2023 , 13 , 2013. [ Google Scholar ] [ CrossRef ]
  • Quílez-Bermejo, J.; Morallón, E.; Cazorla-Amorós, D. Metal-free heteroatom-doped carbon-based catalysts for ORR: A critical assessment about the role of heteroatoms. Carbon 2020 , 165 , 434–454. [ Google Scholar ] [ CrossRef ]
  • Peng, Y.; Liu, H. Effects of Oxidation by Hydrogen Peroxide on the Structures of Multiwalled Carbon Nanotubes. Ind. Eng. Chem. Res. 2006 , 45 , 6483–6488. [ Google Scholar ] [ CrossRef ]
  • Fujita, S.-I.; Watanabe, H.; Katagiri, A.; Yoshida, H.; Arai, M. Nitrogen and oxygen-doped metal-free carbon catalysts for chemoselective transfer hydrogenation of nitrobenzene, styrene, and 3-nitrostyrene with hydrazine. J. Mol. Catal. A Chem. 2014 , 393 , 257–262. [ Google Scholar ] [ CrossRef ]
  • Zhao, A.; Masa, J.; Schuhmann, W.; Xia, W. Activation and Stabilization of Nitrogen-Doped Carbon Nanotubes as Electrocatalysts in the Oxygen Reduction Reaction at Strongly Alkaline Conditions. J. Phys. Chem. C 2013 , 117 , 24283–24291. [ Google Scholar ] [ CrossRef ]
  • Paraknowitsch, J.P.; Thomas, A. Doping carbons beyond nitrogen: An overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications. Energy Environ. Sci. 2013 , 6 , 2839–2855. [ Google Scholar ] [ CrossRef ]
  • Zhong, H.; Zhang, H.; Xu, Z.; Tang, Y.; Mao, J. A Nitrogen-Doped Polyaniline Carbon with High Electrocatalytic Activity and Stability for the Oxygen Reduction Reaction in Fuel Cells. ChemSusChem 2012 , 5 , 1698–1702. [ Google Scholar ] [ CrossRef ]
  • Bosilj, M.; Rustam, L.; Thomann, R.; Melke, J.; Fischer, A.; White, R.J. Directing nitrogen-doped carbon support chemistry for improved aqueous phase hydrogenation catalysis. Catal. Sci. Technol. 2020 , 10 , 4794–4808. [ Google Scholar ] [ CrossRef ]
  • Villora-Picó, J.J.; Pastor-Blas, M.M.; Sepúlveda-Escribano, A. N-Doped Activated Carbons from Polypyrrole-Effect of Steam Activation Conditions. Chem. Ing. Tech. 2021 , 94 , 94–100. [ Google Scholar ] [ CrossRef ]
  • Zeng, L.; Li, X.; Fan, S.; Mu, J.; Qin, M.; Wang, X.; Gan, G.; Tadé, M.; Liu, S. Seaweed-Derived Nitrogen-Rich Porous Biomass Carbon as Bifunctional Materials for Effective Electrocatalytic Oxygen Reduction and High-Performance Gaseous Toluene Absorbent. ACS Sustain. Chem. Eng. 2019 , 7 , 5057–5064. [ Google Scholar ] [ CrossRef ]
  • Su, C.; Guo, Y.; Chen, H.; Zou, J.; Zeng, Z.; Li, L. VOCs adsorption of resin-based activated carbon and bamboo char: Porous characterization and nitrogen-doped effect. Colloids Surfaces A Physicochem. Eng. Asp. 2020 , 601 , 124983. [ Google Scholar ] [ CrossRef ]
  • Villora-Picó, J.-J.; Coloma-Pascual, F.; Sepúlveda-Escribano, A.; Pastor-Blas, M.M. N-doped activated carbons obtained from polyaniline for toluene and water adsorption. Inorg. Chem. Commun. 2024 , 167 , 112684. [ Google Scholar ] [ CrossRef ]
  • Niu, J.; Zhang, H.; Li, L.; Guo, Y. Cost-effective activated carbon (AC) production from partial substitution of coal with red mud (RM) as additive for SO2 and NOx abatement at low temperature. Fuel 2021 , 293 , 120448. [ Google Scholar ] [ CrossRef ]
  • Kang, K.Y.; Lee, B.I.; Lee, J.S. Hydrogen adsorption on nitrogen-doped carbon xerogels. Carbon 2009 , 47 , 1171–1180. [ Google Scholar ] [ CrossRef ]
  • Liu, Z.; Du, Z.; Song, H.; Wang, C.; Subhan, F.; Xing, W.; Yan, Z. The fabrication of porous N-doped carbon from widely available urea formaldehyde resin for carbon dioxide adsorption. J. Colloid Interface Sci. 2013 , 416 , 124–132. [ Google Scholar ] [ CrossRef ]
  • Shen, Y.; Zhang, N. A facile synthesis of nitrogen-doped porous carbons from lignocellulose and protein wastes for VOCs sorption. Environ. Res. 2020 , 189 , 109956. [ Google Scholar ] [ CrossRef ]
  • Zhu, L.; Shen, D.; Luo, K.H. A critical review on VOCs adsorption by different porous materials: Species, mechanisms and modification methods. J. Hazard. Mater. 2020 , 389 , 122102. [ Google Scholar ] [ CrossRef ]
  • Liu, S.; Cui, L.; Peng, Z.; Wang, J.; Hu, Y.; Yu, A.; Wang, H.; Peng, P.; Li, F.-F. Eco-friendly synthesis of N,S co-doped hierarchical nanocarbon as a highly efficient metal-free catalyst for the reduction of nitroarenes. Nanoscale 2018 , 10 , 21764–21771. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Kiciński, W.; Szala, M.; Bystrzejewski, M. Sulfur-doped porous carbons: Synthesis and applications. Carbon 2014 , 68 , 1–32. [ Google Scholar ] [ CrossRef ]
  • Gao, Z.; Zhang, Y.; Li, D.; Werth, C.J.; Zhang, Y.; Zhou, X. Highly active Pd–In/mesoporous alumina catalyst for nitrate reduction. J. Hazard. Mater. 2015 , 286 , 425–431. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Deng, W.; Zhang, Y.; Yang, L.; Tan, Y.; Ma, M.; Xie, Q. Sulfur-doped porous carbon nanosheets as an advanced electrode material for supercapacitors. RSC Adv. 2015 , 5 , 13046–13051. [ Google Scholar ] [ CrossRef ]
  • Chacón, F.J.; Cayuela, M.L.; Roig, A.; Sánchez-Monedero, M.A. Understanding, measuring and tuning the electrochemical properties of biochar for environmental applications. Rev. Environ. Sci. Bio/Technology 2017 , 16 , 695–715. [ Google Scholar ] [ CrossRef ]
  • Hasegawa, G.; Deguchi, T.; Kanamori, K.; Kobayashi, Y.; Kageyama, H.; Abe, T.; Nakanishi, K. High-Level Doping of Nitrogen, Phosphorus, and Sulfur into Activated Carbon Monoliths and Their Electrochemical Capacitances. Chem. Mater. 2015 , 27 , 4703–4712. [ Google Scholar ] [ CrossRef ]
  • Yan, Z.; Gao, L.; Dai, C.; Zhang, M.; Lv, X.; Shen, P.K. Metal-free mesoporous carbon with higher contents of active N and S codoping by template method for superior ORR efficiency to Pt/C. Int. J. Hydrogen Energy 2018 , 43 , 3705–3715. [ Google Scholar ] [ CrossRef ]
  • Hua, Y.; Jiang, T.; Wang, K.; Wu, M.; Song, S.; Wang, Y.; Tsiakaras, P. Efficient Pt-free electrocatalyst for oxygen reduction reaction: Highly ordered mesoporous N and S co-doped carbon with saccharin as single-source molecular precursor. Appl. Catal. B Environ. 2016 , 194 , 202–208. [ Google Scholar ] [ CrossRef ]
  • Yue, W.; Yu, Z.; Zhang, X.; Liu, H.; He, T.; Ma, X. Green activation method and natural N/O/S co-doped strategy to prepare biomass-derived graded porous carbon for supercapacitors. J. Anal. Appl. Pyrolysis 2024 , 178 , 106409. [ Google Scholar ] [ CrossRef ]
  • Wu, W.; Wu, C.; Liu, J.; Yan, H.; Li, G.; Zhao, Y.; Bei, K.; Zhang, G. Synergistic effects of heteroatom doping and narrow micropores on carbon dioxide capture in bamboo shoot shell-based porous carbon. Sep. Purif. Technol. 2024 , 339 , 126690. [ Google Scholar ] [ CrossRef ]
  • Bide, Y.; Jahromi, N.N. Nitrogen and sulfur dual doped porous carbon as metal-free catalyst for oxidative degradation of 4-nitrophenol by persulfate activation. Sci. Rep. 2023 , 13 , 1212. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Villora-Picó, J.-J.; Sepúlveda-Escribano, A.; Pastor-Blas, M.-M. Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene. Int. J. Mol. Sci. 2024 , 25 , 2515. [ Google Scholar ] [ CrossRef ]
  • Hussain, N.; Alwan, S.; Alshamsi, H.; Sahib, I. Green Synthesis of S- and N-Codoped Carbon Nanospheres and Application as Adsorbent of Pb (II) from Aqueous Solution. Int. J. Chem. Eng. 2020 , 2020 , 1–13. [ Google Scholar ] [ CrossRef ]
  • Tao, K.; Fu, S.; Yang, M.; Zhang, N.; Liu, K.; Liu, W.; Zhou, Y.; Li, S.; Sun, J. Nitrogen and sulfur co-doped carbon-coated Li 4 Ti 5 O 12 composite to enhance lithium storage properties. Ionics 2024 , 30 , 2083–2091. [ Google Scholar ] [ CrossRef ]
  • Zhong, G.; Yang, H.; Zeng, M.; Liu, S.; Chen, S.; Fan, Z.; Zhu, C.; Xu, J.; Yu, J. Enabling Heteroatom Doping of Flexible MXene Film in Seconds: A Microwave-Induced Targeted Thermal-Shock Method. Adv. Funct. Mater. 2024 , 34 , 2313845. [ Google Scholar ] [ CrossRef ]
  • Horikawa, T.; Sakao, N.; Sekida, T.; Hayashi, J.; Do, D.; Katoh, M. Preparation of nitrogen-doped porous carbon by ammonia gas treatment and the effects of N-doping on water adsorption. Carbon 2011 , 50 , 1833–1842. [ Google Scholar ] [ CrossRef ]
  • Luo, W.; Wang, B.; Heron, C.G.; Allen, M.J.; Morre, J.; Maier, C.S.; Stickle, W.F.; Ji, X. Pyrolysis of Cellulose under Ammonia Leads to Nitrogen-Doped Nanoporous Carbon Generated through Methane Formation. Nano Lett. 2014 , 14 , 2225–2229. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Skudin, V.; Andreeva, T.; Myachina, M.; Gavrilova, N. CVD-Synthesis of N-CNT Using Propane and Ammonia. Materials 2022 , 15 , 2241. [ Google Scholar ] [ CrossRef ]
  • Wei, Q.; Tong, X.; Zhang, G.; Qiao, J.; Gong, Q.; Sun, S. Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions. Catalysts 2015 , 5 , 1574–1602. [ Google Scholar ] [ CrossRef ]
  • Villora-Picó, J.-J.; Gil-Muñoz, G.; Sepúlveda-Escribano, A.; Pastor-Blas, M.M. Doped activated carbons obtained from nitrogen and sulfur-containing polymers as metal-free catalysts for application in nitroarenes hydrogenation. Int. J. Hydrogen Energy 2024 , 53 , 490–502. [ Google Scholar ] [ CrossRef ]
  • Hu, X.; Sun, X.; Song, Q.; Zhu, Y.; Long, Y.; Dong, Z. N,S co-doped hierarchically porous carbon materials for efficient metal-free catalysis. Green Chem. 2019 , 22 , 742–752. [ Google Scholar ] [ CrossRef ]
  • Pan, F.; Li, B.; Deng, W.; Du, Z.; Gang, Y.; Wang, G.; Li, Y. Promoting electrocatalytic CO2 reduction on nitrogen-doped carbon with sulfur addition. Appl. Catal. B Environ. 2019 , 252 , 240–249. [ Google Scholar ] [ CrossRef ]
  • Bubanale, S.; Shivashankar, M.; Siddaganga Institute of Technology. History, Method of Production, Structure and Applications of Activated Carbon. Int. J. Eng. Res. 2017 , V6 , 495–498. [ Google Scholar ] [ CrossRef ]
  • Sekirifa, M.L.; Hadj-Mahammed, M.; Pallier, S.; Baameur, L.; Richard, D.; Al-Dujaili, A.H. Preparation and characterization of an activated carbon from a date stones variety by physical activation with carbon dioxide. J. Anal. Appl. Pyrolysis 2013 , 99 , 155–160. [ Google Scholar ] [ CrossRef ]
  • Dastgheib, S.A.; Salih, H.; Ilangovan, T.; Mock, J. NO Oxidation by Activated Carbon Catalysts: Impact of Carbon Characteristics, Pressure, and the Presence of Water. ACS Omega 2020 , 5 , 21172–21180. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Wu, W.; Wu, C.; Zhang, G.; Liu, J.; Li, Y.; Li, G. Synthesis and characterization of magnetic K2CO3-activated carbon produced from bamboo shoot for the adsorption of Rhodamine b and CO2 capture. Fuel 2023 , 332 , 126107. [ Google Scholar ] [ CrossRef ]
  • Hassani, S.S.; Ganjali, M.R.; Samiee, L.; Rashidi, A.M.; Tasharrofi, S.; Yadegari, A.; Shoghi, F.; Martel, R. Comparative Study of Various Types of Metal-Free N and S Co-Doped Porous Graphene for High Performance Oxygen Reduction Reaction in Alkaline Solution. J. Nanosci. Nanotechnol. 2018 , 18 , 4565–4579. [ Google Scholar ] [ CrossRef ]
  • Mansour, S.A. Thermal decomposition of calcium citrate tetrahydrate. Thermochim. Acta 1994 , 233 , 243–256. [ Google Scholar ] [ CrossRef ]
  • Chalermnon, M.; Cherdchom, S.; Sereemaspun, A.; Rojanathanes, R.; Khotavivattana, T. Biguanide-Based Synthesis of 1,3,5-Triazine Derivatives with Anticancer Activity and 1,3,5-Triazine Incorporated Calcium Citrate Nanoparticles. Molecules 2021 , 26 , 1028. [ Google Scholar ] [ CrossRef ]
  • Lee, S.; Choi, J.; Chung, Y.S.; Kim, J.; Moon, S.; Lee, S. Understanding the catalytic mechanism of calcium compounds for enhancing crystallinity in carbon fiber. Chem. Eng. J. 2024 , 479 , 147728. [ Google Scholar ] [ CrossRef ]
  • Li, X.; Kurasch, S.; Kaiser, U.; Antonietti, M. Synthesis of Monolayer-Patched Graphene from Glucose. Angew. Chem. Int. Ed. 2012 , 51 , 9689–9692. [ Google Scholar ] [ CrossRef ]
  • Wang, K.; Li, Q.; Liu, B.; Cheng, B.; Ho, W.; Yu, J. Sulfur-doped g-C 3 N 4 with enhanced photocatalytic CO 2 -reduction performance. Appl. Catal. B Environ. 2015 , 176 , 44–52. [ Google Scholar ] [ CrossRef ]
  • Ojha, N.; Bajpai, A.; Kumar, S. Visible light-driven enhanced CO 2 reduction by water over Cu modified S-doped g-C 3 N 4 . Catal. Sci. Technol. 2019 , 9 , 4598–4613. [ Google Scholar ] [ CrossRef ]
  • Pan, F.; Jin, J.; Fu, X.; Liu, Q.; Zhang, J. Advanced Oxygen Reduction Electrocatalyst Based on Nitrogen-Doped Graphene Derived from Edible Sugar and Urea. ACS Appl. Mater. Interfaces 2013 , 5 , 11108–11114. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Shcherban, N.D.; Filonenko, S.M.; Ovcharov, M.L.; Mishura, A.M.; Skoryk, M.A.; Aho, A.; Murzin, D.Y. Simple method for preparing of sulfur–doped graphitic carbon nitride with superior activity in CO 2 photoreduction. ChemistrySelect 2016 , 1 , 4987–4993. [ Google Scholar ] [ CrossRef ]
  • Guo, X.; Wang, R.; Ni, L.; Qiu, S.; Zhang, Z. Synthesis of Li 4 Ti 5 O 12 with Tunable Morphology Using l-Cysteine and Its Enhanced Lithium Storage Properties. Chempluschem 2018 , 84 , 123–129. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Tsubouchi, N.; Ohtsuka, Y. Nitrogen release during high temperature pyrolysis of coals and catalytic role of calcium in N2 formation. Fuel 2002 , 81 , 2335–2342. [ Google Scholar ] [ CrossRef ]
  • Ejaz, A.; Jeon, S. The individual role of pyrrolic, pyridinic and graphitic nitrogen in the growth kinetics of Pd NPs on N-rGO followed by a comprehensive study on ORR. Int. J. Hydrogen Energy 2018 , 43 , 5690–5702. [ Google Scholar ] [ CrossRef ]
  • Liu, P.; Gao, S.; Wang, Y.; Huang, Y.; He, W.; Huang, W.; Luo, J. Carbon nanocages with N-doped carbon inner shell and Co/N-doped carbon outer shell as electromagnetic wave absorption materials. Chem. Eng. J. 2019 , 381 , 122653. [ Google Scholar ] [ CrossRef ]
  • Ferrero, G.; Sevilla, M.; Fuertes, A. Mesoporous carbons synthesized by direct carbonization of citrate salts for use as high-performance capacitors. Carbon 2015 , 88 , 239–251. [ Google Scholar ] [ CrossRef ]
  • Bokobza, L.; Bruneel, J.-L.; Couzi, M. Raman Spectra of Carbon-Based Materials (from Graphite to Carbon Black) and of Some Silicone Composites. C J. Carbon Res. 2015 , 1 , 77–94. [ Google Scholar ] [ CrossRef ]
  • Ferrari, A.C.; Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 2000 , 61 , 14095–14107. [ Google Scholar ] [ CrossRef ]
  • Cho, S.-R.; Cho, H.-G. Characterization of Black Carbon Collected from Candle Light and Automobile Exhaust Pipe. J. Korean Chem. Soc. 2013 , 57 , 691–696. [ Google Scholar ] [ CrossRef ]
  • Ayiania, M.; Weiss-Hortala, E.; Smith, M.; McEwen, J.-S.; Garcia-Perez, M. Microstructural analysis of nitrogen-doped char by Raman spectroscopy: Raman shift analysis from first principles. Carbon 2020 , 167 , 559–574. [ Google Scholar ] [ CrossRef ]
  • Thommes, M.; Kaneko, K.; Neimark, A.V.; Olivier, J.P.; Rodriguez-Reinoso, F.; Rouquerol, J.; Sing, K.S.W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 2015 , 87 , 1051–1069. [ Google Scholar ] [ CrossRef ]
  • Hu, X.; Long, Y.; Fan, M.; Yuan, M.; Zhao, H.; Ma, J.; Dong, Z. Two-dimensional covalent organic frameworks as self-template derived nitrogen-doped carbon nanosheets for eco-friendly metal-free catalysis. Appl. Catal. B Environ. 2018 , 244 , 25–35. [ Google Scholar ] [ CrossRef ]
  • Liu, N.; Song, H.; Chen, X. Morphology control of ordered mesoporous carbons by changing HCl concentration. J. Mater. Chem. 2011 , 21 , 5345–5351. [ Google Scholar ] [ CrossRef ]
  • Yang, Y.; Gu, L.; Guo, S.; Shao, S.; Li, Z.; Sun, Y.; Hao, S. N-Doped Mesoporous Carbons: From Synthesis to Applications as Metal-Free Reduction Catalysts and Energy Storage Materials. Front. Chem. 2019 , 7 , 761. [ Google Scholar ] [ CrossRef ]
  • Lv, Q.; Si, W.; He, J.; Sun, L.; Zhang, C.; Wang, N.; Yang, Z.; Li, X.; Wang, X.; Deng, W.; et al. Selectively nitrogen-doped carbon materials as superior metal-free catalysts for oxygen reduction. Nat. Commun. 2018 , 9 , 3376. [ Google Scholar ] [ CrossRef ]
  • Han, Y.; Yan, D.; Ma, Z.; Wang, Q.; Wang, X.; Li, Y.; Sun, G. Lignin-derived sulfonate base metal-free N, S co-doped carbon microspheres doped with different nitrogen sources as catalysts for oxygen reduction reactions. Int. J. Biol. Macromol. 2023 , 244 , 125363. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Shu, Y.; Takada, Y.; Takada, R.; Taniguchi, Y.; Miyake, K.; Uchida, Y.; Kong, C.Y.; Nishiyama, N. Experimental and Theoretical Elucidation of Metal-Free Sulfur and Nitrogen Co-Doped Porous Carbon Materials with an Efficient Synergistic Effect on the Oxygen Reduction Reaction. Adv. Mater. Interfaces 2023 , 10 , 2300088. [ Google Scholar ] [ CrossRef ]
  • Sun, P.; Wang, X.; Zhu, M.; Ahmad, N.; Zhang, K.; Xu, X. Nitrogen Self-Doped Metal Free Catalysts Derived from Chitin via One Step Method for Efficient Electrocatalytic CO 2 Reduction to CO. Catalysts 2023 , 13 , 904. [ Google Scholar ] [ CrossRef ]
  • Liu, Z.; Peng, F.; Wang, H.; Yu, H.; Zheng, W.; Yang, J. Phosphorus-Doped Graphite Layers with High Electrocatalytic Activity for the O 2 Reduction in an Alkaline Medium. Angew. Chem. Int. Ed. 2011 , 50 , 3257–3261. [ Google Scholar ] [ CrossRef ]
  • Yang, L.; Jiang, S.; Zhao, Y.; Zhu, L.; Chen, S.; Wang, X.; Wu, Q.; Ma, J.; Ma, Y.; Hu, Z. Boron-Doped Carbon Nanotubes as Metal-Free Electrocatalysts for the Oxygen Reduction Reaction. Angew. Chem. Int. Ed. 2011 , 50 , 7132–7135. [ Google Scholar ] [ CrossRef ]
  • Yang, D.-S.; Bhattacharjya, D.; Inamdar, S.; Park, J.; Yu, J.-S. Phosphorus-Doped Ordered Mesoporous Carbons with Different Lengths as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media. J. Am. Chem. Soc. 2012 , 134 , 16127–16130. [ Google Scholar ] [ CrossRef ]
  • Quílez-Bermejo, J.; González-Gaitán, C.; Morallón, E.; Cazorla-Amorós, D. Effect of carbonization conditions of polyaniline on its catalytic activity towards ORR. Some insights about the nature of the active sites. Carbon 2017 , 119 , 62–71. [ Google Scholar ] [ CrossRef ]
  • Rangraz, Y.; Heravi, M.M. Recent advances in metal-free heteroatom-doped carbon heterogonous catalysts. RSC Adv. 2021 , 11 , 23725–23778. [ Google Scholar ] [ CrossRef ]
  • Zhang, Q.; Zhang, D.; Zhou, Y.; Qian, J.; Wen, X.; Jiang, P.; Ma, L.; Lu, C.; Feng, F.; Li, X. Preparation of Heteroatom-Doped Carbon Materials and Applications in Selective Hydrogenation. ChemistrySelect 2022 , 7 , e202102581. [ Google Scholar ] [ CrossRef ]
  • Denis, P.A.; Faccio, R.; Mombru, A.W. Is It Possible to Dope Single-Walled Carbon Nanotubes and Graphene with Sulfur? Chemphyschem 2009 , 10 , 715–722. [ Google Scholar ] [ CrossRef ]
  • Graphene, S.; Catalyst, M.C.; Reduction, O. Sulfur-Doped Graphene as an E ffi cient Metal-free Cathode Catalyst for. ACS Nano 2012 , 6 , 205–211. [ Google Scholar ]
  • Gao, K.; Wang, B.; Tao, L.; Cunning, B.V.; Zhang, Z.; Wang, S.; Ruoff, R.S.; Qu, L. Efficient Metal-Free Electrocatalysts from N-Doped Carbon Nanomaterials: Mono-Doping and Co-Doping. Adv. Mater. 2018 , 31 , e1805121. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Pan, F.; Duan, Y.; Zhang, X.; Zhang, J. A Facile Synthesis of Nitrogen/Sulfur Co-Doped Graphene for the Oxygen Reduction Reaction. ChemCatChem 2015 , 8 , 163–170. [ Google Scholar ] [ CrossRef ]
  • Liang, C.; Wang, Y.; Li, T. Synthesis of sulfur-doped p-type graphene by annealing with hydrogen sulfide. Carbon 2015 , 82 , 506–512. [ Google Scholar ] [ CrossRef ]
  • Li, X.; Lau, S.P.; Tang, L.; Ji, R.; Yang, P. Sulphur doping: A facile approach to tune the electronic structure and optical properties of graphene quantum dots. Nanoscale 2014 , 6 , 5323–5328. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Liang, J.; Jiao, Y.; Jaroniec, M.; Qiao, S.Z. Sulfur and Nitrogen Dual-Doped Mesoporous Graphene Electrocatalyst for Oxygen Reduction with Synergistically Enhanced Performance. Angew. Chem. Int. Ed. 2012 , 51 , 11496–11500. [ Google Scholar ] [ CrossRef ]
  • Li, W.; Bandosz, T.J. Role of Heteroatoms in S,N-Codoped Nanoporous Carbon Materials in CO 2 (Photo)electrochemical Reduction. ChemSusChem 2018 , 11 , 2987–2999. [ Google Scholar ] [ CrossRef ] [ PubMed ]
  • Qu, K.; Zheng, Y.; Jiao, Y.; Zhang, X.; Dai, S.; Qiao, S. Polydopamine-Inspired, Dual Heteroatom-Doped Carbon Nanotubes for Highly Efficient Overall Water Splitting. Adv. Energy Mater. 2016 , 7 , 1602068. [ Google Scholar ] [ CrossRef ]
  • Lu, C.; Zhu, Q.; Zhang, X.; Ji, H.; Zhou, Y.; Wang, H.; Liu, Q.; Nie, J.; Han, W.; Li, X. Decoration of Pd Nanoparticles with N and S Doped Carbon Quantum Dots as a Robust Catalyst for the Chemoselective Hydrogenation Reaction. ACS Sustain. Chem. Eng. 2019 , 7 , 8542–8553. [ Google Scholar ] [ CrossRef ]
  • Bag, S.; Mondal, B.; Das, A.K.; Raj, C.R. Nitrogen and Sulfur Dual-Doped Reduced Graphene Oxide: Synergistic Effect of Dopants Towards Oxygen Reduction Reaction. Electrochimica Acta 2015 , 163 , 16–23. [ Google Scholar ] [ CrossRef ]
  • Dinadayalane, T.; Lazare, J.; Alzaaqi, N.F.; Herath, D.; Hill, B.; Campbell, A.E. Structures, Properties, and Applications of Nitrogen-Doped Graphene , 1st ed.; Elsevier B.V.: Amsterdam, The Netherlands, 2022; Volume 21. [ Google Scholar ] [ CrossRef ]
  • Wang, H.; Maiyalagan, T.; Wang, X. Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications. ACS Catal. 2012 , 2 , 781–794. [ Google Scholar ] [ CrossRef ]
  • Biddinger, E.J.; von Deak, D.; Ozkan, U.S. Nitrogen-Containing Carbon Nanostructures as Oxygen-Reduction Catalysts. Top. Catal. 2009 , 52 , 1566–1574. [ Google Scholar ] [ CrossRef ]
  • Yang, X.; Chen, D.; Liao, S.; Song, H.; Li, Y.; Fu, Z.; Su, Y. High-performance Pd–Au bimetallic catalyst with mesoporous silica nanoparticles as support and its catalysis of cinnamaldehyde hydrogenation. J. Catal. 2012 , 291 , 36–43. [ Google Scholar ] [ CrossRef ]

Click here to enlarge figure

Carbon SampleCHNS
MELCIT51.721.4117.850.00
CYSCIT62.451.746.977.61
Carbon SampleC 1sO 1sS 2pCa 2pN 1s
MELCIT73.806.480.001.5718.15
CYSCIT86.354.51.750.157.24
Carbon SampleI /I
MELCIT1.41
CYSCIT1.02
SampleV (cm /g)V (cm /g)V (cm /g)S (m /g)
MELCIT0.150.050.099126
CYSCIT1.380.331.05856
SampleV (N ) (cm /g)V (CO ) (cm /g)
MELCIT0.050.55
CYSCIT0.330.20
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Villora-Picó, J.-J.; Gil-Muñoz, G.; Sepúlveda-Escribano, A.; Pastor-Blas, M.M. The Facile Production of p -Chloroaniline Facilitated by an Efficient and Chemoselective Metal-Free N/S Co-Doped Carbon Catalyst. Int. J. Mol. Sci. 2024 , 25 , 9603. https://doi.org/10.3390/ijms25179603

Villora-Picó J-J, Gil-Muñoz G, Sepúlveda-Escribano A, Pastor-Blas MM. The Facile Production of p -Chloroaniline Facilitated by an Efficient and Chemoselective Metal-Free N/S Co-Doped Carbon Catalyst. International Journal of Molecular Sciences . 2024; 25(17):9603. https://doi.org/10.3390/ijms25179603

Villora-Picó, Juan-José, Gema Gil-Muñoz, Antonio Sepúlveda-Escribano, and M. Mercedes Pastor-Blas. 2024. "The Facile Production of p -Chloroaniline Facilitated by an Efficient and Chemoselective Metal-Free N/S Co-Doped Carbon Catalyst" International Journal of Molecular Sciences 25, no. 17: 9603. https://doi.org/10.3390/ijms25179603

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  • Published: 03 September 2024

Nano silica-mediated stabilization of heavy metals in contaminated soils

  • Maryam Samani 1 ,
  • Yogesh K. Ahlawat 2 ,
  • Ahmad Golchin 1 ,
  • Hossein Ali Alikhani 3 ,
  • Arzhang Fathi-Gerdelidani 3 ,
  • Umang Ahlawat 4 ,
  • Anurag Malik 5 ,
  • Reetika Panwar 6 ,
  • Deva Shri Maan 7 ,
  • Meraj ahmed 8 ,
  • Princy Thakur 8 &
  • Sadhna Mishra 9  

Scientific Reports volume  14 , Article number:  20496 ( 2024 ) Cite this article

Metrics details

  • Biogeochemistry
  • Environmental sciences

Soil contamination with heavy metals presents a substantial environmental peril, necessitating the exploration of innovative remediation approaches. This research aimed to investigate the efficiency of nano-silica in stabilizing heavy metals in a calcareous heavy metal-contaminated soil. The soil was treated with five nano-silica levels of 0, 100, 200, 500, and 1000 mg/kg and incubated for two months. The results showed that nano-silica had a specific surface area of 179.68  \({\text{m}}^{2}/\text{g}\) . At 1000 mg/kg, the DTPA-extractable concentrations of Pb, Zn, Cu, Ni, and Cr decreased by 12%, 11%, 11.6%, 10%, and 9.5% compared to the controls, respectively. Additionally, as the nano-silica application rate increased, both soil pH and specific surface area increased. The augmentation of nano-silica adsorbent in the soil led to a decline in the exchangeable (EX) and carbonate-bound fractions of Pb, Cu, Zn, Ni, and Cr, while the distribution of heavy metals in fractions bonded with Fe–Mn oxides, organic matter, and residue increased. The use of 1000 mg/kg nano-silica resulted in an 8.0% reduction in EX Pb, 4.5% in EX Cu, 7.3% in EX Zn, 7.1% in EX Ni, and 7.9% in EX Cr compared to the control treatment. Overall, our study highlights the potential of nano silica as a promising remediation strategy for addressing heavy metal pollution in contaminated soils, offering sustainable solutions for environmental restoration and ecosystem protection.

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Introduction.

Soil, a critical component of the ecosystem, significantly affects the health of plants, animals, and humans. In the ongoing battle against environmental pollution, soil contamination with heavy metals presents a significant challenge, threatening both ecosystems and human health. The behavior of heavy metals in soils varies with soil type, and composition, and over time, with chemical reactions often reducing their bioavailability and solubility. Unlike organic pollutants, heavy metals remain in the soil for long periods, resisting chemical and microbial decomposition, necessitating their relocation, removal, or impact reduction 1 . Traditional remediation methods often fail to effectively address the complex nature of heavy metal contamination in soils. However, emerging technologies are offering innovative and sustainable solutions to remediate heavy metal-contaminated soils.

A cost-effective method for mitigating heavy metal contamination in soil is immobilization 2 . This environmentally friendly approach aims to prevent toxic compounds from entering biological cycles by reducing their solubility or toxicity 3 . Immobilization involves mixing contaminated soil with suitable compounds, which induces changes in pH, specific surface area (SSA), ion exchange, adsorption, and stabilization processes, thereby reducing the mobility and toxicity of pollutants 4 . Various soil components, such as silicate minerals, organic matter, clay minerals, and iron and manganese oxides, can trap heavy metals in their lattice structures or form bonds with them. The strength of these bonds affects the retention or release of heavy metals from the soil 5 .

Heavy metals in soils exist in different geochemical forms. The distribution of these geochemical forms in soils varies based on pH, cation exchange capacity, soil texture, redox state, organic matter, lime, and Fe–Mn oxide contents 6 . An understanding of the distribution of heavy metals among these various geochemical forms is crucial in determining their solubility, availability, and toxicity in the soil 7 . The sequential extraction method 5 serves as a valuable tool for identifying the chemical forms of heavy metals and assessing their bioavailability 8 .

The traditional stabilizers for the immobilization of heavy metals include lime, hydroxyapatite, zeolite, phosphates 9 , bentonite 10 , fly ash and red mud, and so on 11 . Furthermore, new materials, such as nano-materials 12 , biochar 13 , 14 , polymer 15 and modified material 16 are also used as stabilizer to remediate heavy metal contaminated soils. These stabilizers can reduce the activity of heavy metals in soils to a certain extent, but their specificity and long-term stability are not enough, and their influence on soil properties has not been detected, which limits their large-scale application. Therefore, it is necessary to develop a new stabilizer with strong specificity, long-term stability and few adverse effects on soil environment.

Silica or functionalized silica can be used as an adsorbent to remove heavy metals from aqueous systems and to immobilize them in soil. Silica is an inorganic solid that is made of a three-dimensional network structure and a porous structure with a very large surface area. Silica is mainly composed of siloxane groups (Si–O–Si) inside and silanol groups (Si–OH) on the particle surface. Silanol groups can be separated into three types (single classified silanol), geminal (binary), and adjacent silanol. Silanol groups located on the surface of silica easily react with various agents. Many properties such as adsorption, adhesion, catalytic, and chemical properties of silica depend on the chemistry of these surface groups 17 . In addition to the surface, silanol groups may also be found inside the silica skeleton. Silanol groups are hydrophilic and siloxanes are hydrophobic 18 .

Nanoparticles are used in many sciences. Many nanoparticles have very different properties from micro and macro materials. The main reason for using nanoparticles is their very small size and large specific surface area, which play an important role in chemical reactions. Nanoparticles are widely used in the stabilization of heavy metals in soils due to their high adsorption capacity, high reactivity, and unsaturated surfaces. Silicon dioxide modified nanoparticles have been used in some studies as a sorbent to remediate heavy metals in soil and alleviate the stress of heavy metals on plants. For example, Zhang 19 reported that the application of modified nano-silica transformed Cu, Pb, and Zn to a more stable fraction in soil. Lian 20 indicated that the nano-silica decreased the DTPA-extractable Cd in soil effectively. However, the application rates of nano-silica in their research were much higher than an acceptable rate for large-scale applications (the maximum application rate is 6%). In recent years, research on the application of nano-silica for the removal or stabilization of heavy metals in aquatic environments 21 , 22 , 23 , 24 , 25 , 26 and functionalized nano-silica for the stabilization of heavy metals in soils 27 , 28 , 29 , 30 at high rates economically unfeasible has shown promising results. However, the use of un-functionalized silica nanoparticles for the remediation of heavy metals in complex soil environments, especially at economically feasible rates, has been relatively overlooked. Building on this foundation, a new study has been conducted to explore using un-functionalized silica nanoparticles to stabilize heavy metals in soil. This innovative approach not only aims to improve the efficiency of metal stabilization but also seeks to understand the impact of nano-silica on soil properties and the re-distribution of metals within different soil solid phases.

The goals of this research include (i) investigating the influences of un-functionalized nano-silica on specific surface area and pH of calcareous soil as two important soil factors affecting the sorption and availability of heavy metals, (ii) assessing the effectiveness of un-functionalized nano-silica in stabilizing heavy metals in calcareous soil, and (iii) unraveling the mechanisms underlying the stabilization of heavy metals by un-functionalized nano-silica. By shedding light on these aspects, the study provides valuable insights into the potential of un-functionalized nano-silica for the remediation of heavy metal-contaminated soils.

Materials and methods

Soil analysis.

A composite soil sample at a depth of 0–15 cm was collected from an urban park located in Tehran, Iran. The sample was air-dried at room temperature, passed through a 2 mm sieve, analyzed for physico-chemical properties, and used for this study. Soil texture was determined by the hydrometer method 31 . The pH at a 1:5 soil-to-water ratio and the electrical conductivity of saturated paste extract (ECe) were measured using a pH meter and an EC meter, respectively 32 , 33 . Organic carbon and calcium carbonate contents in the soil were measured by using Walkley–Black 34 and the Calcimetry methods 35 . Cation exchange capacity (CEC) was determined using the sodium acetate method 36 , and specific surface area (SSA) was measured by BET. The available fractions of heavy metals in the soil were extracted by DTPA 37 , and their concentrations were determined using ICP-MS. Total concentration of heavy metals in the soil was measured by ICP-MS after aqua regia digestion 38 .

Soil amendment

Nano-silica with a chemical formula \({\text{SiO}}_{2}\) and a purity of 99.5% was prepared by Pasargad Novin Chemical Company. Some characteristics of the prepared nano-silica were determined using XRF, XRD, SEM, FTIR, and BET techniques.

Pot experiment

To investigate the effect of nano-silica on the immobilization of Pb, Zn, Cu, Ni, and Cr in the soil, a pot experiment was conducted under greenhouse conditions using a completely randomized design and three replications. The nano-silica was mixed with three kg of urban soil at five rates of 0, 100, 200, 500, and 1000 mg nano-silica per kg soil. Treated and untreated (control) soil samples were incubated for two mouths at the moisture of field capacity. At the end of the incubation period, treated and untreated soil samples were air-dried at room temperature and used to evaluate the impacts of different levels of nano-silica on available and chemical fractions of Pb, Zn, Cu, Ni, and Cr in the soil.

Sequential extraction

Chemical fractions of heavy metals were determined in treated and untreated soil samples by the sequential extraction method 5 . This procedure partitions the total content of heavy metal into five fractions: exchangeable (EX), bound to carbonates (CAR), bound to Fe–Mn oxides (OX), bound to organic matter (OM), and residual (RES). Each fraction was extracted by a special extractant at a given time and temperature presented in Table 1 .

Statistical analysis

The experimental data were analyzed using the SPSS 21.0 statistical software package and Microsoft Excel 2016. The experiment was conducted based on a completely randomized design (CRD) with three replicates for each treatment. The treatments included five nano-silica levels of 0, 100, 200, 500, and 1000 mg/kg. A one-way ANOVA was performed to determine the effect of different levels of nano-silica on each response variable. The means for each treatment group were compared using Duncan’s multiple range test at a significance level of P  < 0.05.

Results and discussion

Soil characteristics.

Some physico-chemical properties of the soil used in this study are summarized in Table 2 . The studied soil was non-saline, calcareous, poor in OC content, and with a basic pH and a silty loam texture.

Nano-silica characteristics

Xrf analysis.

The results of the chemical analysis of nano-silica by XRF are shown in Table 3 . Silica nanoparticles have more than 99% silicon dioxide, and the impurities include Fe and Na, with amounts less than 20 and 50 mg/kg, respectively. Calcium and Ti are also present, with values less than 70 and 120 mg/kg, respectively.

XRD analysis

The XRD pattern of silica nano adsorbent is shown in Fig.  1 . Intense peaks at 22.15 and 44.3 angles indicate the presence of \({\text{SiO}}_{2}\) crystal structure in the tetragonal crystal system. Parameters a, b, and c are determined as 4.7, 4.7, and 7.4, respectively. Among other crystallographic parameters of this material, we can mention alpha, beta, and gamma, all of which are 90° (Fig.  1 ).

figure 1

The XRD pattern of nano-silica. Crystallin structure in tetragonal crystal system.

The SEM image

The surface morphology of silica particles determined by a scanning electron microscope (SEM) is shown in Fig.  2 . Silica nanoparticles have a spherical shape.

figure 2

SEM image of nano-silica.

The FTIR spectrum

FTIR analysis was used to determine surface functional groups affecting adsorption. The FTIR spectrum of silica nanoparticles is shown in Fig.  3 . The strong peaks in the regions of 471.04, 812.12, and 1138.25  \({\text{cm}}^{-1}\) are related to the asymmetric stretching vibrations of siloxane groups (Si–O–Si). The peak in the region of 3427.6  \({\text{cm}}^{-1}\) corresponds to the vibrational stretching of the O–H group, which overlaps with the silanol (Si–OH) group 39 , 40 .

figure 3

FTIR spectrum showing Siloxan (Si–O–Si), O–H and Silanol (Si–OH) groups in nano-silica.

BET specific surface area

Based on the results of the BET technique, the adsorption and desorption curve of nano-silica is type IV, indicating the mesoporous structure of silica. Silica nanoparticles have a specific surface area of 179.68  \({\text{m}}^{2}/\text{g}\) and the percentage of porosity is 93.95% (Fig.  4 a). The mesopore volume and diameter are obtained from the BJH curve. According to the BJH curve, the total volume and diameter of the nano-silica pores were 0.397  \({\text{cm}}^{3}/\text{g}\) and 2.42 nm, respectively (Fig.  4 b).

figure 4

( a ) Adsorption/desorption isotherm used to calculate the specific surface area of nano-silica using the BET technique. ( b ) BJH plot used to calculate the total volume and the diameter of the nano-silica pores using the BET technique.

The nano-silica effect on soil pH

The results of The nano-silica effects on soil pH are presented in Fig.  5 . The results showed that application of nano-silica caused an increase in soil pH compared to the control treatment. The pH value increased from 7.43 in the control to 7.87 and 7.88 with the application of 500 and 1000 mg of silica per kg of soil, respectively. pH is one of the important factors in controlling the balance between heavy metal solution in soil 41 . Previous reports indicated that the addition of Si-based materials changed the pH of the soil 42 , which was observed in the present research.

figure 5

The effect of different nano-silica levels on soil pH.

The nano-silica effect on the DTPA-extractable concentrations of metals

The mean comparison results of the effects of different nano-silica levels on the DTPA extractable concentration of heavy metals showed that the highest available concentration of metals was in the control treatment, while the lowest available concentration of metals was in the 1000 mg/kg Nano-silica treatment (Fig.  6 ).

figure 6

The effect of different nano-silica levels on concentration of DTPA heavy metals. For each metal, means with a common letter are not significantly different (P \(<\) 0.05).

The highest and lowest concentrations of DTPA extractable Pb were 7.54 and 6.63 mg/kg, with a 12% decrease observed when applying 1000 mg/kg of nano-silica compared to the control treatment. For Zn and Cu, the highest concentrations found in the control treatment were 27.12 and 7.75 mg/kg, respectively, while the lowest concentrations observed in the 1000 mg/kg treatment were 24.08 and 6.85 mg/kg, resulting in an 11% decrease for Zn and an 11.6% decrease for Cu compared to the control. Similarly, for Ni and Cr, the highest concentrations found in the control treatment were 6.24 and 9.42 mg/kg, respectively, and the lowest concentrations observed in the 1000 mg/kg treatment were 5.61 and 8.52 mg/kg, corresponding to a 10% decrease for Ni and a 9.5% decrease for Cr compared to the control treatment. Overall, the most significant reduction in the available concentration of heavy metals in the tested soil was observed for Pb, followed by Cu, Zn, Ni, and Cr ( 4 ).

Unique properties exist between different heavy metal ions, such as ionic radius, electronegativity, and hydration radius 43 . Previous studies have shown that these intrinsic properties are inseparable from the adsorption properties of heavy metal ions, and the adsorption stability and adsorption energy are also affected by them 43 . In a study conducted by Pan 43 , they stated the modified biomass-based adsorption technique has attracted much attention in heavy metal ions removal, a carboxylated biogas residue (BR–COOH) was prepared to remove the \({\text{Cu}}^{2+}\) and \({\text{Zn}}^{2+}\) from single/binary heavy metal ions solution and explore selective adsorption mechanism. The results exhibited that the adsorption capacities of BR–COOH for \({\text{Cu}}^{2+}\) was higher than that for \({\text{Zn}}^{2+}\) obviously, whether in the single or binary heavy metal ions solution. Meanwhile, the inconsistency in the change of adsorption capacity for \({\text{Cu}}^{2+}\) and \({\text{Zn}}^{2+}\) also confirmed that differences in affinity exist between BR–COOH and different heavy metal ions, and \({\text{Cu}}^{2+}\) seems to be more readily captured. The maximum adsorption capability of \({\text{Cu}}^{2+}\) was visibly higher than that of \({\text{Zn}}^{2+}\) , indicating that the \({\text{Cu}}^{2+}\) preferentially adsorbed to the carboxyl functional groups and occupied the active sites at the same time. The adsorbed \({\text{Cu}}^{2+}\) was unable to be exchanged into solution by \({\text{Zn}}^{2+}\) . They also reported the adsorbed quantities of these metal ions followed the order of \({\text{Hg}}^{2+}\) > \({\text{Cu}}^{2+}\) > \({\text{Pb}}^{2+}\) > \({\text{Fe}}^{2+}\) > \({\text{Cd}}^{2+}\) > \({\text{Zn}}^{2+}\) > \({\text{Mn}}^{2+}\)  >  \({\text{Mg}}^{2+}\) . The difference in the amounts of Pb, Cu and Zn adsorbed may be due to the acid–base theory. Pb belongs to hard acids and tends to complex with hydroxy (hard base) groups on the surface of silica more than Cu and Zn. Thus, Pb is more prone to immobilization than Cu and Cd 44 . The amount of specific adsorption of ions on solid surfaces depends largely on the electric charge, the hydration radius of the ions, the sealing energy, and the electronegativity of the ions. Reducing the hydrated radius and energy, and increasing the electronegativity increases the tendency to ion-specific adsorption 45 . The reason for the higher adsorption of Pb and Cu ions than Zn is likely due to the lower hydrated radius of the Pb (0.401 nm), and Cu (0.419 nm) compared to the Zn (0.43 nm) and their higher electronegativity 46 , 47 . Pan 43 stated that \({\text{Cu}}^{2+}\)  was more easily adsorbed onto carboxylated biosorbent than \({\text{Zn}}^{2+}\) .

In the present study, it was observed that soil pH increased with increasing the application level of nano-silica, but the concentration of DTPA-extractable Cr decreased from 9.4 mg/kg in the control treatment to 8.5 mg/kg at the highest nano-silica application level. A negative correlation between soil pH and heavy metal mobility in soil and bioavailability to plants has been well documented in the literature 48 . However, the effect of soil pH on Cr sorption/desorption in soil varies with its chemical form and oxidation state. Chromium in soil exists in two common oxidation states: Cr(III), and Cr (VI). In the Cr(III) valence state, Cr is a metal cation (as the free \({\text{Cr}}^{3+}\) species or as a hydrolysis product: \({\text{CrOH}}^{2+}\) or \({\text{Cr}(\text{OH})}_{2}^{+}\) depending on solution pH). In the Cr (VI) state, Cr occurs in the chromate species: \({\text{HCrO}}_{4}^{-}\) and \({\text{CrO}}_{4}^{2-}\) 49 . Thus, increasing soil pH has a contrary effect on the sorption of Cr(III) and Cr (VI) species. The sorption of Cr(III) on soil solids increases with an increase in pH, while Cr (VI) sorption on soil particles decreases with an increase in pH 48 . Nano-silica induced coordination, co-precipitation, and other geochemical behaviors with Cr, which inhibit the increased electrostatic repulsion of Cr (VI) with soil colloids resulted from an increase in soil pH, could be reasons for this decreased DTPA-extractable concentration of Cr observed in the present study 50 , 51 .

It seems that the application of 1000 mg/kg nano-silica provided sufficient surfaces for the adsorption of heavy metals thus decreasing their concentration in the soil solution. The surfaces of nano-silica have hydroxyl active groups that have high adsorption capacity and are in the forms of free silanol (Si–OH) groups, free silanol diol groups ( \({\text{Si}-(\text{OH})}_{2}\) ) and atomic bridges with oxygen ions (Si–O–Si) in surface 17 . Silanol groups on the silica surface react easily with a variety of agents. The adsorption capacity of the silica depends on the charge and electronegativity of the metals; the metal cations in the solution form a chemical bond with the siloxane oxygen attached to the surface of the silica. Both silanol and siloxane groups in the nano-silica surface play a very important role in the adsorption capacity of metals 52 . Lian 20 reported that \({\text{SiO}}_{2}-\text{SH}\) can significantly (P \(<\) 0.05) decrease the heavy metal concentration in the plants, which indicates that the \({\text{SiO}}_{2}-\text{SH}\) can immobilize the heavy metals in the contaminated soil and reduce their phytoavailability. Some Si-based materials have been used to remediate heavy metals in soil and alleviate the stress of heavy metals on plants 13 , 53 .

Zhang 27 reported that the application of modified nano-silica transformed Cu, Pb, and Zn to a more stable fraction in soil. Lian 20 indicated that the nano-silica decreased the DTPA-extractable Cd in soil effectively. Silica nanoparticles ( \({\text{NSiO}}_{2}\) ) are very efficient in removing metal ions due to the surface characteristics of silica 54 . Investigations showed that among various organic and inorganic modifiers, silica nanoparticles are widely used due to their large surface area and suitable places for metal adsorption. Studies on the adsorption of heavy metals Ni, Cd, and Pb by porous silica nanoparticles in aqueous environments have been also carried out. Rezvani-Barojni 55 stated that nano-silica has a high adsorption capacity for Hg and this adsorbent had inhomogeneous adsorption sites that had different adsorption potentials.

The soil pH effect on the DTPA-extractable concentrations of metals

The results showed by increasing the soil pH, the DTPA extractable concentrations of heavy metals decreased (Fig.  7 ). The surface charge of silica increases with increasing pH, and at higher pH, the negative charge of the silica surface causes more metal cations to be adsorbed 56 . An increase in pH causes a decrease in metals in the available fractions of heavy metals and a reduction in their bioavailability in the soil 10 , 57 . Heidari 57 also reported that by increasing the pH of the solution, the adsorption capacity of silica for Ni, Cd, and Pb increased.

figure 7

The pH effect on DTPA-extractable concentrations of heavy metals in the studied soil. For each metal, means with a common letter are not significantly different (P \(<\) 0.05).

In the adsorption process, solution pH is crucial; it influences both the contaminants’ ionization level and the adsorbent’s surface charge 58 . Meky 26 in a study about the pH effect on removing Pb by nano-silica from aqua medium reported when pH falls below 3, the synthesized nano \({\text{SiO}}_{2}\) ’s zeta potential data shows that it has reached the isoelectric point, which is the point at which the positive and negative charges produced by the silanol groups on the surface of the silica particles are equal. The silanol groups with the Si–OH structure are stable at that moment. The zeta potential grows in negative proportion as the pH value rises over 3.5, signifying a rise in the amount of negative charges on the particle surface. The equilibrium of the SiOH/SiO—acid/base dissociation means that an increase in negative charges will lead to an increase in \({\text{SiO}}^{-}\) species and the surface energy 59 . Subsequently, the surface of \({\text{SiO}}_{2}\) is positively charged at any pH value below the pzc and negatively charged at any pH value over the pzc. For Pb (II), when the pH of the solution increases (pH > 3), the surface of the synthesized nano- \({\text{SiO}}_{2}\) becomes negatively charged, and as a result, the adsorption of positively charged Pb (II) is enhanced due to the electrostatic attraction. Ahmad 60 also investigated the effect of silica nanoparticles on Cu adsorption in the aqueous medium and found that by increasing the pH of the solution from 4 to 6.5, the amount of Cu adsorption increased. This shows that at lower pH, the concentration of \({\text{H}}^{+}\) ions is high and these ions are competing with other metal ions to form chelate and complexation in the exchange sites of the silica surface. At higher pH, hydroxyl ions in the reaction medium increase, and metal ions tend to form hydroxide or react with surface hydroxyls.

The nano-silica effect on soil SSA and the relationship between soil SSA and DTPA-extractable concentrations of metals

The application of nano-silica to soil increased its SSA. The soil SSA increased from 19.63 \({\text{m}}^{2}/\text{g}\) in the control treatment to 21.23, 22.83, 24.43, and 26.03  \({\text{m}}^{2}/\text{g}\) with the application of 100, 200, 500, and 1000 mg/kg nano-silica, respectively. Increasing the soil SSA by applying nano-silica reduced the DTPA-extractable concentrations of heavy metals (Fig.  8 ). There was a good correlation coefficient \({\text{R}}^{2}\) between the soil SSA and DTPA extractable concentrations of heavy metals. The R 2 s obtained were obtained were 87% for Pb and Cu > 86% for Zn and Cr > 83% for Ni. The inverse correlation between soil SSA and DTPA extractable concentrations of heavy metals suggests that the increased surface area of the soil due to the application of nano-silica leads to increased adsorption of heavy metals, resulting in a reduction of their concentrations in the solution phase. The higher the amount of nano-silica present, the greater the available surface area provided, leading to increased metal adsorption. Specific surface area is the most effective property in the soil treated with silica Si nanoparticles, leading to many changes in physico-chemical properties 61 , 62 . Bayat 63 reported the positive effects of different nanomaterials on soil surface area using magnesium oxide (MgO).

figure 8

Relationship between the soil SSA and DTPA-extractable concentrations of heavy metals.

A material with a higher SSA can adsorb more heavy metal ions per unit mass compared to a material with a lower surface area. This is because a larger surface area provides more sites for the heavy metal ions to attach to the adsorbent material. Specific surface area is often correlated with the pore structure of the adsorbent material. Materials with higher surface areas tend to have a greater proportion of mesopores and micropores, which can provide additional surface area for adsorption and offer diffusion pathways for heavy metal ions into the material. The SSA influences the kinetics and thermodynamics of the adsorption process. A higher surface area can accelerate the adsorption kinetics by providing more sites for heavy metal ions to interact with the adsorbent material. Additionally, it can enhance the thermodynamic driving force for adsorption, leading to higher adsorption capacities. The high surface area of the silica compared to soil, provided high reactive sites, which allowed metal ions to be adsorbed on them 64 . Silica nanoparticles ( \({\text{SiO}}_{2}\) ) are very efficient in removing metal ions due to the surface characteristics of silica 54 . Investigations showed that among various organic and inorganic modifiers, silica nanoparticles are widely used due to their large surface area and suitable places for metal absorption.

In a study by Al-Saeed 65 on the contribution of nano-silica in affecting some of the physico-chemical properties of cultivated soil, it was noted that varying rates of nano-silica have a significant effect on the percentage of clay particles, cation exchange capacity (CEC), sodium adsorption ratio (SAR), porosity, saturation percentage, SSA, and the concentrations of total nitrogen (N) and silicon ( \({\text{Si}}^{4+}\) ).

The effect of different silica nano levels on the fractionation of heavy metals in soil

The distribution of different geochemical forms of heavy metals Pb, Zn, Cu, Ni and Cr in untreated soil (control treatment) was as follow: CAR (43.79%) > OX (16.98%) > OM (14.49%) > RES (12.78%) > EX (11.1%) for Pb; CAR (45%) > OX (17%) > RES (15.5%) > OM (13.2%) > EX (9.3%) for Zn; CAR \(=\) OX (28.13%) > RES (23.49%) > OM \(=\) EX (10.19%) for Cu; OX (44.8%) > CAR (20.78%) > RES (14.48%) > EX (11.9%) > OM (8.04%) for N; and CAR (40.8%) > OX (18.52%) > RES (15.19%) > OM (14.19%) > EX (11.3%) for Cr (Table  5 and Fig.  9 ).

figure 9

Effect of different nano-silica levels on the distribution of geochemical fractions of heavy metals in the studied soil. F1: Exchangeable, F2: Carbonated bound, F3: Fe/Mn Oxyhydroxide, F4: Organic matter bound, and F5: Residual fraction.

Mean comparisons showed that with increasing the nano-silica application level in the soil, the exchangeable and carbonate-bounded fractions of Pb, Cu, Zn, Ni, and Cr decreased but the Fe–Mn OX, OM, and RES fractions increased (Table 5 and Fig.  9 ).

At the nano-silica application level of 1000 mg/kg, the concentration of the EX and CAR bound fractions of Pb decreased from 6.73 and 26.03 mg/kg in the control treatment to 6.19 and 25.42 mg/kg, accounting for 8.02% and 2.34%, respectively. However, when applying nano-silica at a level of 1000 mg/kg, the concentration of the OX fraction of Pb increased from 10.28 mg/kg in the control treatment to 10.59 mg/kg. Similarly, the concentration of the OM fraction of Pb rose from 8.75 to 8.92 mg/kg, and the concentration of the RES fraction of Pb increased from 8.03 to 8.33 mg/kg. The increase in the concentration of different chemical forms of Pb using silica nanoparticles follows the order: RES (3.73%) > OX (3.01%) > OM (1.94%).

For Cu, by an increase in the amount of nano-silica in the soil, the concentration of EX and CAR fractions of Cu decreased by 4.46% and 2.26%, respectively, compared to the control treatment, so that the concentration of EX fraction of Cu was 6.27 mg/kg in the control treatment reached to 5.99 mg/kg in the 1000 mg/kg nano-silica treatment. The CAR fraction of Cu decreased from 17.22 mg/kg in the control treatment to 16.83 mg/kg in the 1000 mg/kg of nano-silica. In 1000 mg/kg nano-silica, the amount of OX fraction of Cu increased from 17.24 mg/kg in the control treatment to 17.39 mg/kg. The OM fraction of Cu also increased from 6.27 mg/kg in the control treatment to 6.63 mg/kg with the application of nano-silica. Similarly, the Res fraction of Cu increased from 14.44 mg/kg in the control treatment to 14.57 mg/kg. The augmentation of Cu chemical forms through the application of silica nanoparticles followed this order: OM (5.74%) > RES (0.9%) > OX (0.87%).

The concentration of the EX and CAR bound fractions of Pb decreased from 6.27 and 17.22 mg/kg in the control treatment to 5.99 and 16.83 mg/kg at the nano-silica application level of 1000 mg/kg, representing 4.46% and 2.26% reductions, respectively. Conversely, in the 1000 mg/kg nano-silica treatment, the concentration of the OX fraction of Cu increased from 17.24 mg/kg in the control treatment to 17.39 mg/kg.

The concentration of the EX and CAR bound fractions of Zn decreased from 18.68 and 90.42 mg/kg in the control treatment to 17.32 and 88.7 mg/kg at the nano-silica application level of 1000 mg/kg, representing 7.28% and 1.9% reductions, respectively. Conversely, in the 1000 mg/kg nano-silica treatment, the concentration of the OX and Res fractions of Zn increased from 26.52 and 31.14 mg/kg in the control treatment to 26.88 and 31.25 mg/kg, in 1000 mg/kg nano-silica treatment, respectively. The effect of silica nanoparticles on changing the distribution of Zn chemical forms followed as OX (6.76%) > OM (1.35%) > RES (0.35%).

For Ni, the concentration of the EX and CAR bound fractions of Ni decreased from 4.76 and 8.31 mg/kg in the control treatment to 4.42 and 7.97 mg/kg at the nano-silica application level of 1000 mg/kg, corresponding to 7.14% and 4.09% reductions, respectively. Conversely, in the 1000 mg/kg nano-silica treatment, the concentration of the OX and Res fractions of Ni increased from 17.93 and 5.76 mg/kg in the control treatment to 18.26 and 5.96 mg/kg, in 1000 mg/kg nano-silica treatment, respectively. The effect of silica nanoparticles on changing the distribution of Ni chemical forms followed the order OM (6.54%) > RES (3.47%) > OX (1.88%).

For Cr, the concentration of the EX and CAR bound fractions of Cr decreased from 8.87 and 32.03 mg/kg in the control treatment to 8.17 and 31.77 mg/kg at the nano-silica application level of 1000 mg/kg, accounting for 7.9% and 0.8%, respectively. Conversely, in the 1000 mg/kg nano-silica treatment, the concentration of the OX, OM, and Res fractions of Cr increased from 14.53, 11.14, and 12.32 mg/kg in the control treatment to 14.77, 11.22, and 12.47 mg/kg, in 1000 mg/kg nano-silica treatment, respectively. The effect of silica nanoparticles on changing the distribution of Cr chemical forms followed the order OX (1.72%) > RES (1.21%) > OM (0.71%).

In the present study, the exchangeable and carbonate-bounded fractions of heavy metals decreased by using nano-silica. Previous research indicated that the exchangeable and carbonate-bounded fractions of heavy metals usually determine the real environmental risk 14 , which means the addition of nano-silica reduced the risk of heavy metals in the contaminated soil. Similar results have also been reported by Lian 20 and Wang 53 .

Several mechanisms, such as adsorption, complexation, co-precipitation, and changes in soil properties like pH and surface area, have been reported in the literature for the redistribution and immobilization of heavy metals in soils induced by the nanosilica application. Nano-silica has a high specific surface area and can provide numerous active sites for adsorption of heavy metals such as Pb, Cu, Zn, Ni, and Cr through inner-sphere surface complexation 20 , 66 , 67 . The sorption of heavy metals onto \({\text{SiO}}_{2}\) surfaces can reduce their concentrations in the more easily extractable fractions (e.g., exchangeable, and carbonated bound), effectively sequestering them and preventing their leaching or mobility 20 . Heavy metals that are strongly adsorbed to the nano-silica surface will also be associated with the residual fraction, as they become more resistant to extraction 20 . \({\text{SiO}}_{2}\) can also co-precipitate with trace metals, incorporating them into the \({\text{SiO}}_{2}\) mineral structure 66 . The co-precipitation of heavy metals with \({\text{SiO}}_{2}\) can reduce their concentrations in the carbonated bound and Fe–Mn oxide fractions, as the co-precipitated metals will be associated with the residual fraction, which represents the most recalcitrant and structurally incorporated forms of the metals 5 . Nano-silica can alter the soil pH, which can influence the solubility and mobility of heavy metals. A higher pH can lead to the precipitation of metal hydroxides, which can then become associated with Fe/Mn oxyhydroxides 30 . This transformation can result in a decrease in the exchangeable and carbonate bounded fractions as metals are immobilized in less bioavailable forms 30 . The presence of nano-silica can also enhance the binding of heavy metals to organic matter in the soil, as it can act as a bridge between the metal ions and organic functional groups 68 . This results in an increase in the organic matter bounded fraction of heavy metals 53 .

Conclusions

Applying the nano-silica increased the soil pH and SSA but decreased the DTPA-extractable concentrations of heavy metals in the studied calcareous soil. The nano-silica caused a significant decrease in the concentrations of Pb, Cu, Zn, Ni, and Cr in the exchangeable and carbonate-bound fractions, while the distribution of heavy metals in fractions bonded with Fe–Mn oxides, organic matter, and residue increased. The highest effect of silica nano sorbent in reducing the available concentration of heavy metals in the studied soil was Pb > Cu > Zn > Ni > Cr. There was a good correlation coefficient ( \({\text{R}}^{2}\) ) between the soil SSA and DTPA-extractable concentrations of heavy metals. Nano-silica could be used to remediate heavy metal-contaminated agricultural soils. The stabilization mechanism of heavy metals could be attributed to the -SH and -OH bonds of Nano-silica. This study suggests that nano-silica has advantages and potential in the remediation of heavy metal-contaminated agricultural soils.

While nano-silica-mediated stabilization of heavy metals in contaminated soils holds great promise, further research is warranted to address certain aspects and optimize its application. The following future directions could guide ongoing investigations: Understanding the interactions at the nanoscale is essential for tailoring nano-silica to target different contaminants. Transitioning from laboratory experiments to field-scale trials is critical for validating the efficacy of nano-silica under real-world conditions. This step will provide insights into its performance in diverse soil types, climates, and contaminant scenarios. Also, a comprehensive assessment of the ecological impact of nano-silica on non-target organisms, plant growth, and overall soil biodiversity is necessary. This will ensure that the technology does not inadvertently lead to unintended environmental consequences.

Evaluating the economic feasibility of large-scale nano-silica applications is crucial for its practical implementation. Assessing the cost-effectiveness of the technology will contribute to its adoption by regulatory bodies and industries involved in environmental remediation.

Data availability

All data generated or analysed during this study are included in this published article [and its supplementary information files ].

Adriano, D. C. et al. Role of assisted natural remediation in environmental cleanup. Geoderma 122 (2–4), 121–142 (2004).

Article   ADS   CAS   Google Scholar  

Paff, S. W. & Bosilovich, B. E. Use of lead reclamation in secondary lead smelters for the remediation of lead contaminated sites. J. Hazard. Mater. 40 (2), 139–164 (1995).

Article   CAS   Google Scholar  

Malone, P., Jones, L. and Larson, R. Guide to the disposal of chemically stabilized and solidified waste, SW-872. 1982, Office of Water and Waste Management , USEPA. Washington DC, USA.

Stegmann, R., et al. , Treatment of contaminated soil: Fundamentals, analysis, applications. Springer Science & Business Media, (2013).

Tessier, A., Campbell, P. G. & Bisson, M. Sequential extraction procedure for the speciation of particulate trace metals. Anal. Chem. 51 (7), 844–851 (1979).

Zheng, H. et al. Sorption isotherm and kinetic modeling of aniline on Cr-bentonite. J. Hazard. Mater. 167 (1–3), 141–147 (2009).

Article   ADS   CAS   PubMed   Google Scholar  

Adu-Gyamfi, J. et al. Geochemical assessment and pollution evaluation of stream sediments’ quality impacted by industrial activities at Suame Magazine area, Kumasi, Ghana. Arab. J. Geosci. 16 (4), 256 (2023).

Saffari, M. et al. Effect of calcium carbonate removal on the chemical forms of zinc in calcareous soils by three sequential extraction methods. Res. J. Biol. Sci. 4 (7), 858–865 (2009).

Google Scholar  

Xenidis, A., Stouraiti, C. & Papassiopi, N. Stabilization of Pb and As in soils by applying combined treatment with phosphates and ferrous iron. J. Hazard. Mater. 177 (1–3), 929–937 (2010).

Article   CAS   PubMed   Google Scholar  

Sun, Y. et al. In situ stabilization remediation of cadmium (Cd) and lead (Pb) co-contaminated paddy soil using bentonite. Appl. Clay Sci. 105 , 200–206 (2015).

Article   Google Scholar  

Wang, Y. et al. Stabilization of Cd-, Pb-, Cu-and Zn-contaminated calcareous agricultural soil using red mud: A field experiment. Environ. Geochem. Health 40 , 2143–2153 (2018).

Cui, H. et al. Fractions of Cu, Cd, and enzyme activities in a contaminated soil as affected by applications of micro-and nanohydroxyapatite. J. Soils Sedim. 13 , 742–752 (2013).

Lu, H. et al. Influences of calcium silicate on chemical forms and subcellular distribution of cadmium in Amaranthus hypochondriacus L.. Sci. Rep. 7 (1), 40583 (2017).

Article   ADS   CAS   PubMed   PubMed Central   Google Scholar  

Hamzenejad Taghlidabad, R. & Sepehr, E. Heavy metals immobilization in contaminated soil by grape-pruning-residue biochar. Arch. Agron. Soil Sci. 64 (8), 1041–1052 (2018).

Yuan, Y.-N. et al. Application of polymeric aluminum salts in remediation of soil contaminated by Pb, Cd, Cu, and Zn. J. Central South Univ. 20 (6), 1638–1644 (2013).

Chen, W.-F. et al. Investigation of heavy metal (Cu, Pb, Cd, and Cr) stabilization in river sediment by nano-zero-valent iron/activated carbon composite. Environ. Sci. Pollut. Res. 23 , 1460–1470 (2016).

Zhuravlev, L. The surface chemistry of amorphous silica Zhuravlev model. Colloids Surf. A Phys. Eng. Asp. 173 (1–3), 1–38 (2000).

Wagh, P. & Ingale, S. Comparison of some physico-chemical properties of hydrophilic and hydrophobic silica aerogels. Ceram. Int. 28 (1), 43–50 (2002).

Zhang, L.-Y., et al. , Effects of heavy metals pollution on paddy soil aggregates composition and heavy metals distribution . Yingyong Shengtai Xuebao , 20 (11), (2009).

Lian, M. et al. Highly effective immobilization of Pb and Cd in severely contaminated soils by environment-compatible, mercapto-functionalized reactive nanosilica. J. Clean. Prod. 235 , 583–589 (2019).

Kumar, R., Rauwel, P. & Rauwel, E. Nanoadsorbants for the removal of heavy metals from contaminated water: Current scenario and future directions. Processes 9 (8), 1379 (2021).

Bai, L. et al. Synthesis of a novel silica-supported dithiocarbamate adsorbent and its properties for the removal of heavy metal ions. J. Hazard. Mater. 195 , 261–275 (2011).

Salmani, M. H. et al. Synthesis, characterization and application of mesoporous silica in removal of cobalt ions from contaminated water. Groundw. Sustain. Dev. 11 , 100425 (2020).

Al-Saida, B. et al. Synthesis of nanosilica for the removal of multicomponent Cd2+ and Cu2+ from synthetic water: An experimental and theoretical study. Molecules 27 (21), 7536 (2022).

Article   CAS   PubMed   PubMed Central   Google Scholar  

Al-Wasidi, A. S. et al. Modification of silica nanoparticles with 1-hydroxy-2-acetonaphthone as a novel composite for the efficient removal of Ni (II), Cu (II), Zn (II), and Hg (II) ions from aqueous media. Arab. J. Chem. 15 (8), 104010 (2022).

Meky, N. et al. Synthesis of nano-silica oxide for heavy metal decontamination from aqueous solutions. Water, Air, Soil Pollut. 235 (2), 154 (2024).

Zhang, L. et al. Speciation analysis and speciation transformation of heavy metal ions in passivation process with thiol-functionalized nano-silica. Chem. Eng. J. 369 , 979–987 (2019).

Wang, Y. et al. Long-term stabilization of Cd in agricultural soil using mercapto-functionalized nano-silica (MPTS/nano-silica): A three-year field study. Ecotoxicol. Environ. Saf. 197 , 110600 (2020).

Wang, Y. et al. Effect of surface-modified nano-silica on the mobility and fraction of Cd in contaminated agricultural soils. Soil Sedim. Contam. An Int. J. 29 (1), 96–106 (2020).

Lei, C. et al. Immobilization of Pb and Zn in contaminated soil using alumina-silica nano-amendments synthesized from coal fly ash. Int. J. Environ. Res. Public Health 19 (23), 16204 (2022).

Gee, G. W. & Bauder, J. W. Particle-size analysis. Methods Soil Anal. Part 1 Phys. Mineral. Methods 5 , 383–411 (1986).

Thomas, G. W. Soil pH and soil acidity. Methods Soil Anal. Part 3 Chem. Methods 5 , 475–490 (1996).

Rhoades, J., Salinity: Electrical conductivity and total dissolved solids . Methods Soil Anal. Part 3—Chem. Methods, 417–435 (1996).

Walkley, A. & Black, I. A. An examination of the Degtjareff method for determining soil organic matter, and a proposed modification of the chromic acid titration method. Soil Sci. 37 (1), 29–38 (1934).

Helmke, P. A. & Sparks, D. L. Lithium, sodium, potassium, rubidium, and cesium. Methods Soil Anal. Part 3 Chem. Methods 5 , 551–574 (1996).

Bower, C. & Hatcher, J. Simultaneous determination of surface area and cation-exchange capacity. Soil Sci. Soc. Am. J. 30 (4), 525–527 (1966).

Lindsay, W. L. & Norvell, W. Development of a DTPA soil test for zinc, iron, manganese, and copper. Soil Sci. Soc. Am. J. 42 (3), 421–428 (1978).

Soon, Y. and Abboud, S. Cadmium, chromium, lead and nickel. 1993, Chap.

Lin, J. et al. Immobilization of cadmium in polluted soils by phytogenic iron oxide nanoparticles. Sci. Total Environ. 659 , 491–498 (2019).

Ramezani, M., Vaezi, M. R. & Kazemzadeh, A. Preparation of silane-functionalized silica films via two-step dip coating sol–gel and evaluation of their superhydrophobic properties. Appl. Surf. Sci. 317 , 147–153 (2014).

Malandrino, M. et al. Accumulation of heavy metals from contaminated soil to plants and evaluation of soil remediation by vermiculite. Chemosphere 82 (2), 169–178 (2011).

Ji, X. et al. Effect of silicon fertilizers on cadmium in rice ( Oryza sativa ) tissue at tillering stage. Environ. Sci. Pollut. Res. 24 , 10740–10748 (2017).

Pan, J. et al. Insights into selective adsorption mechanism of copper and zinc ions onto biogas residue-based adsorbent: Theoretical calculation and electronegativity difference. Sci. Total Environ. 805 , 150413 (2022).

Chaturvedi, P. K., Seth, C. S. & Misra, V. Sorption kinetics and leachability of heavy metal from the contaminated soil amended with immobilizing agent (humus soil and hydroxyapatite). Chemosphere 64 (7), 1109–1114 (2006).

Vico, L. Acid–base behaviour and Cu2+ and Zn2+ complexation properties of the sepiolite/water interface. Chem. Geol. 198 (3–4), 213–222 (2003).

Nightingale, E. Jr. Phenomenological theory of ion solvation. Effective radii of hydrated ions. J. Phys. Chem. 63 (9), 1381–1387 (1959).

Abd-Elfattah, A. & Wada, K. Adsorption of lead, copper, zinc, cobalt, and cadmium by soils that differ in cation-exchange materials. J. Soil Sci. 32 (2), 271–283 (1981).

Shahid, M. et al. Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: A review. Chemosphere 178 , 513–533 (2017).

Essington, M. E., Soil and water chemistry: an integrative approach. CRC press (2015).

Lyu, P. et al. Ternary Ca–Mg–Al layered double-hydroxides for synergistic remediation of As, Cd, and Pb from both contaminated soil and groundwater: Characteristics, effectiveness, and immobilization mechanisms. J. Hazard. Mater. 442 , 130030 (2023).

Article   PubMed   Google Scholar  

Lyu, P. et al. Magnetic biochar-supported layered double hydroxide for simultaneous remediation of As and Cd in soil: Effectiveness, retention durability, and insight into a new immobilization mechanism. J. Clean. Prod. 434 , 140136 (2024).

Flores-Cano, J. V. et al. Adsorption of heavy metals on diatomite: Mechanism and effect of operating variables. Adsorpt. Sci. Technol. 31 (2–3), 275–291 (2013).

Wang, D. et al. Stabilization of Cd-contaminated agricultural soils by modified nano-silica. Environ. Chem 38 (5), 1106–1112 (2019).

CAS   Google Scholar  

Huang, H. et al. Preparation and characterization of octyl and octadecyl-modified mesoporous SBA-15 silica molecular sieves for adsorption of dimethyl phthalate and diethyl phthalate. Microporous Mesoporous Mater. 111 (1–3), 254–259 (2008).

Rezvani-Boroujeni, A. et al. Adsorption properties of thiol-functionalized silica nanoparticles prepared for application in poly (ether sulfone) nanocomposite membranes. J. Text. Polym. 5 (1), 37–47 (2017).

Barisik, M. et al. Size dependent surface charge properties of silica nanoparticles. J. Phys. Chem. C 118 , 1836 (2014).

Heidari, A., Younesi, H. & Mehraban, Z. Removal of Ni (II), Cd (II), and Pb (II) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica. Chem. Eng. J. 153 (1–3), 70–79 (2009).

Kuang, Y., Zhang, X. & Zhou, S. Adsorption of methylene blue in water onto activated carbon by surfactant modification. Water 12 (2), 587 (2020).

Xu, P. et al. Preparation and morphology of SiO 2/PMMA nanohybrids by microemulsion polymerization. Colloid Polym. Sci. 284 , 755–762 (2006).

Ahmad, P. et al. Mitigation of sodium chloride toxicity in Solanum lycopersicum L. by supplementation of jasmonic acid and nitric oxide. J. Plant Interact. 13 (1), 64–72 (2018).

Ghormade, V., Deshpande, M. V. & Paknikar, K. M. Perspectives for nano-biotechnology enabled protection and nutrition of plants. Biotechnol. Adv. 29 (6), 792–803 (2011).

Pérez-Hernández, H. et al. Effect of engineered nanoparticles on soil biota: Do they improve the soil quality and crop production or jeopardize them?. Land Degrad. Dev. 31 (16), 2213–2230 (2020).

Bayat, H. et al. Iron and magnesium nano-oxide effects on some physical and mechanical properties of a loamy Hypocalcic Cambisol. Geoderma 335 , 57–68 (2019).

Little, D. N. and Nair, S. Recommended practice for stabilization of subgrade soils and base materials . (2009).

Al-Saeedi, A. H. Contribution of nano-silica in affecting some of the physico-chemical properties of cultivated soil with the common bean (Phaseolus vulgaris). J. Adv. Agric. Res. 25 (4), 389–400 (2020).

Yadav, M., George, N. and Dwibedi, V. Emergence of toxic trace elements in plant environments: Insights into potential of silica nanoparticles for mitigation of metal toxicity in plants . Environ. Pollut. , 122112 (2023).

Morsy, H. Y. et al. Nano-silica synthesis, characterization and their effects on rice production in the presence of calcium humate under salinity soil stress. World J. Agric. Sci. 19 (5), 189–203 (2023).

Liang, L., Luo, L. & Zhang, S. Adsorption and desorption of humic and fulvic acids on SiO2 particles at nano-and micro-scales. Colloids Surf A: Physicochem Eng Asp. 384 (1–3), 126–130 (2011).

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Maryam Samani & Ahmad Golchin

Centre of Research Impact and Outcome, Chitkara University Institute of Engineering and Technology, Chitkara University, Rajpura, 140401, Punjab, India

Yogesh K. Ahlawat

Soil Science Department, Faculty of Agriculture, University of Tehran, Karaj, Iran

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Kingston Imperial Institute, Dehradun, Uttarakhand, 248007, India

Umang Ahlawat

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Anurag Malik

Department of Horticulture, College of Agriculture, CCS Haryana Agricultural University, Hisar, Haryana, 125004, India

Reetika Panwar

Department of Horticulture, Tantia University Sri Ganganagar, Sri Ganganagar, India

Deva Shri Maan

Department of Soil Science, School of Agriculture, Lovely Professional University, Phagwara, India

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M.S., A.G., and H.A.A.; Writing-original draft, Visualization, Methodology, Investigation, Formal analysis, Data curation, Conceptualization. A.F.G., and Y.K.A, A.M, U.A, R.P, D.S.M, M.A, P.T, S.M.; Writing-review & editing, Methodology, Investigation, Data curation, Conceptualization. A.G., and H.A.A.; Supervision, Project administration, Funding acquisition. All authors have read and agreed to the published version of the manuscript.

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Samani, M., Ahlawat, Y.K., Golchin, A. et al. Nano silica-mediated stabilization of heavy metals in contaminated soils. Sci Rep 14 , 20496 (2024). https://doi.org/10.1038/s41598-024-69182-0

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calcium carbonate and nitric acid experiment

IMAGES

  1. Nitric Acid and Calcium/Sodium Carbonate Reaction

    calcium carbonate and nitric acid experiment

  2. Nitric Acid Reacts With Calcium Carbonate Balanced Equation

    calcium carbonate and nitric acid experiment

  3. Calcium Carbonate and Nitric Acid

    calcium carbonate and nitric acid experiment

  4. Nitric Acid Reacts With Calcium Carbonate Balanced Equation

    calcium carbonate and nitric acid experiment

  5. calcium carbonate and nitric acid reaction

    calcium carbonate and nitric acid experiment

  6. HNO3+CaCO3=H2O+CO2+Ca(NO3)2 Balanced Equation||Nitric acid+Calcium carbonate=Water+Carbon dioxide+

    calcium carbonate and nitric acid experiment

VIDEO

  1. Nitration of Salicylic Acid by Green Approach

  2. NCERT Class 12|chemistry practical |salt analysis-04|CaCO3|Calcium Carbonate

  3. Sodium Carbonate and Calcium Chloride Reaction

  4. Make Nitric Acid at Home

  5. Pembuatan NITRIC ACID bahan pelebur LOGAM MULIA

  6. Reaction of Acid and Carbonate

COMMENTS

  1. Testing salts for anions and cations

    Hydrochloric acid solution, 0.4 mol dm -3; Barium chloride solution, 0.1 mol dm -3 ; Limewater solution, 0.02 mol dm -3 ; Nitric acid, 0.4 mol dm -3; Silver nitrate solution, 0.1 mol dm -3 ; Unknown substances labelled A, B, C …each might contain one of the following anions and one of the following cations:

  2. Reactions of metals with acids producing salts

    The experiment is done first on a smaller scale using test tubes (lesson 1 below), with no attempt to recover the salts formed. This establishes that hydrogen production is a characteristic property of the reaction of metals and acids. It can then be done on a larger scale (lesson 2 below), and the salts formed can be recovered by crystallisation.

  3. Preparation of calcium nitrate

    Calcium nitrate is a complex fertiliser. This simple salt is a source of two nutrients calcium and - nitrogen. Calcium nitrate is manufactured by one of these processes: • the reaction of calcium carbonate (usually as limestone) with nitric acid: CaCO. 3 + 2HNO. 3 Ca(NO. 3) 2 + CO. 2 + H. 2. O • as a by-product of the extraction of ...

  4. acids and carbonates

    This page looks at the reactions between acids and carbonates to give a salt, carbon dioxide and water. A summary equation. acid + carbonate salt + CO2 + water. Reactions involving calcium carbonate. The commonest carbonate-acid reaction you will come across is that between calcium carbonate and dilute hydrochloric acid.

  5. A laboratory study of the heterogeneous reaction of nitric acid on

    A laboratory study of the heterogeneousreaction of nitric acid on calcium carbonateparticles. Abstract. It hasbeen postulated that the reaction of nitricacid with calcium carbonate, namely, CaCO3(s)+ 2HNO3(g)-0 Ca(NO3)2(s) + CO2(g)+ H20(g), playsan importantrole in the atmosphere.

  6. Reaction of Acid and Carbonate (+ test for carbon dioxide gas)

    In this experiment, we will look at the reaction of hydrochloric acid and calcium carbonate to form calcium chloride salt, carbon dioxide, and water.Test for...

  7. Core Practical: Investigating Rate of Reaction

    Diagram: Diagram showing the apparatus needed to investigate the effect of concentration on the rate of reaction. Method: Measure 50 cm 3 of sodium thiosulfate solution into a flask. Measure 5 cm 3 of dilute hydrochloric acid into a measuring cylinder. Draw a cross on a piece of paper and put it underneath the flask.

  8. Calcium carbonate reacts with nitric acid #experiment # ...

    Calcium carbonate reacts with nitric acid to produce calcium nitrate, water and carbon dioxide gas.. Calcium carbonate actually is one of the most common che...

  9. Kinetics of Heterogeneous Reaction of CaCO3 Particles with Gaseous HNO3

    Heterogeneous reaction kinetics of gaseous nitric acid (HNO 3) with calcium carbonate (CaCO 3) particles was investigated using a particle-on-substrate stagnation flow reactor (PS-SFR).This technique utilizes the exposure of substrate deposited, isolated, and narrowly dispersed particles to a gas mixture of HNO 3 /H 2 O/N 2, followed by microanalysis of individual reacted particles using ...

  10. Loss of mass of Marble due to reaction with Nitric Acid

    A sample of marble chips is massed on an analytical balance. The chips, calcium carbonate, will be allowed to react with nitric acid to form carbon dioxide, water, and soluble calcium nitrate. This will result in a noticeable loss of mass. The chips are poured into a beaker, and nitric acid solution is added. The beaker is viewed two hours later.

  11. Testing for negative ions

    Nitric acid is an irritant. (See CLEAPSS Hazcard HC067) Silver nitrate solution can stain skin and clothes. (See CLEAPSS Hazcard HC087) Procedure CO 3 2- carbonate. Put a small amount of limewater into a test (no more than 1 cm 3). Put your sample in a separate test tube and add a few drops of hydrochloric acid.

  12. Rate of Reaction

    Method 2 - Mass of the reaction vessel. Measure 0.40 g of calcium carbonate into a weighing boat; Add 50 cm 3 of dilute hydrochloric acid to a conical flask; Place the conical flask of hydrochloric acid AND the weighing boat of calcium carbonate onto the balance; Measure the combined mass and record this as the t = 0 result Add the 0.40 g of calcium carbonate into the conical flask, replace ...

  13. 3:15 practical: investigate the effect of changing the surface area of

    An investigation of the reaction between marble chips and hydrochloric acid: Marble chips, calcium carbonate (CaCO 3) react with hydrochloric acid (HCl) to produce carbon dioxide gas. Calcium chloride solution is also formed. Using the apparatus shown the change in mass of carbon dioxide can be measure with time.

  14. PMMA (Polymethyl Methacrylate)

    When selecting chips for microfluidic applications, ensuring chemical resistance is crucial for maintaining system integrity and performance. PMMA (Polymethyl Methacrylate) is a popular choice due to its optically clear nature, lightweight properties, and shatter-resistant characteristics. It is commonly used in medical, pharmaceutical, and food processing applications because of its excellent ...

  15. Investigating the Potential of Microbially Induced Carbonate ...

    Based on these findings, we prepared an acidic solution with a pH of 5.6 by mixing sulfuric acid and nitric acid in a 1:1 molar ratio. This mixture was designed to mimic the toxic leaching characteristics experienced under acid rain conditions, providing a realistic scenario for our experiments.

  16. Impacts of interactions with low-mineralized water on permeability and

    The carbonate material in the rock matrix has a typical chemical composition with a strong predominance of calcium oxide (55% on average). The chemical composition of the newly formed calcite crystals is characterized by a slightly increased content of magnesium impurities (0.31% MgO compared to the 0.21% content in the matrix calcite).

  17. Acid-base back titration

    The flask containing hydrochloric acid and calcium carbonate may get warm. Instruct learners to take care not to spill solutions, particularly phenolphthalein, on their skin. If they do get any on their skin, rinse well. Fill the burette at eye level. Equipment. Do the experiment individually or as a pair/small group. Each learner/group will ...

  18. Lipid emulsion attenuates vasodilation by decreasing intracellular

    Lipid emulsion (LE), a widely used parenteral nutrition, exhibits a well-documented ability to reverse the vasodilatory effects induced by acetylcholine in blood vessels. However, the specific mechanisms underlying this action are not yet fully understood. This study aimed to elucidate the mechanism by which LE reverses vasodilation in vitro through dose-response curve experiments, calcium ...

  19. IJMS

    Between 300 and 550 °C, calcium citrate decomposes, producing a calcium aconitate intermediate that evolves into calcium carbonate. Beyond 600 °C, the decomposition of calcium carbonate into carbon monoxide and carbon dioxide is produced, which leaves a residue formed by calcium oxide and carbon [ 82 , 83 ].

  20. Nano silica-mediated stabilization of heavy metals in contaminated

    Ahmad, P. et al. Mitigation of sodium chloride toxicity in Solanum lycopersicum L. by supplementation of jasmonic acid and nitric oxide. J. Plant Interact. 13 (1), 64-72 (2018).