Yudu County, Ganzhou, Jiangxi, China sales3@ar-reagent.com 3170906422@qq.com
Follow us:



Magnesium for Grignard Reactions: Foundation and Future

From Early Chemical Curiosity to Backbone of Modern Synthesis

Magnesium has shaped organic chemistry ever since Victor Grignard found a way to coax reactivity from a humble strip of metal in the late 19th century. His discovery in 1900, which earned a Nobel Prize, unlocked new routes in carbon-carbon bond formation, anchoring the Grignard reagent as a key tool in building complex molecules. As someone who stared down flasks fizzing with ether and magnesium filings while chasing yields in a crowded undergraduate lab, I know firsthand both the excitement and frustration that comes from harnessing this metal’s stubborn nature. Magnesium’s participation in these reactions forms the core of thousands of synthetic pathways. Pharmaceutical innovators and researchers experimenting with new organic scaffolds both owe a debt to the early tinkerers who cracked the code on magnesium’s usefulness.

Magnesium: What’s in the Metal?

Magnesium for Grignard reactions doesn’t just arrive on the bench like any other laboratory commodity. High purity is essential because small traces of oxide or other contaminants can leave researchers watching their allyl bromide swirl in silence, instead of fizzing to life. The shiny silvery appearance of magnesium slips away quickly as it reacts with the atmosphere—a bit of a pain for chemists who value clean reactions. In the right form, fine turnings or even a sand-like powder, magnesium reacts well with halides to generate the classic organomagnesium halides, but this only happens if the metal exposes enough clean surface and isn’t choked with a passivating oxide coating. Chemically, it sits snug between calcium and aluminum on the periodic table, with a standard atomic weight of 24.3. Its standard electrode potential plays a practical role: magnesium reduces most organic halides with ease, pushing the reaction forward every time the surface meets its partner under dry, inert conditions.

Labeling, Purity, and the Hands-On Reality of Activation

People browsing a shelf for magnesium intended for research expect a label noting purity, often 99% or better, and maybe a reminder about storage in sealed containers. Discussions about technical specs sometimes miss the tactile reality that those filings, ribbons, or beads demand handling with care and planning. In real research, chemists often wash the metal with acid or use an initiator like iodine to encourage stubborn pieces to react, because a small handful of magnesium can spell the difference between a one-hour or a three-hour synthesis. Based on my experiences, no one should underestimate the impact of pre-treatment: removing oxide layers with a brief acid dip or scratching the surface gives noticeably better yields, especially in research where every milligram of product matters.

Preparation Method: From Ore to Reaction Flask

Magnesium production kicks off with ores like magnesite, followed by methods like electrolysis and the Pidgeon process to deliver the metal familiar to chemists. Once refined, shaping the metal into turnings, powder, or small bars depends on what synthesis demands. Fine magnesium powder sparks up reactions quickly, but larger turnings offer a slower, steady release where more control is needed. Chemists seeking optimal results often combine mechanical preparation (like using a mortar and pestle) and chemical activation to coax out the very best from the metal. By the time it lands in a flask with dry ether swirling around it, the journey from earth to laboratory feels far from a formality—every step in preparation ripples through to the chemist’s end result.

Reactivity and Modification: Why Every Chemist Sweats the Details

Grignard reactions ask for more than the right ingredients on a bench. The interaction between magnesium and organic halides drives critical bond-forming steps, producing compounds that can be marched forward to alcohols, acids, and even more complex targets. Substituted Mg can enter the mix, and clever changes to the halide or solvent prompt a range of possible reaction routes and products. Magnesium’s behavior changes if a chemist swaps ethereal solvents for THF or dabbles with substrates bearing difficult functional groups, sometimes giving wild swings in reactivity. This constant unpredictability keeps training programs and publications alive with new discoveries—each experiment nudges us toward better control and new chemical landscapes.

Synonyms and Alternate Product Names

People in the lab world refer to magnesium by different names: magnesium turnings, magnesium ribbon, magnesium granules. Old catalogs sometimes whisper of “reagent magnesium” while newer listings call out “activated magnesium” to signal better performance. Whatever the name, the chemical symbol Mg unites all these forms in one periodic table slot, but clear naming on storage shelves cuts out confusion for anyone running a late-night prep.

Safety and Operational Hazards

Anyone who has dropped magnesium into an ether flask knows a little caution goes a long way. Magnesium’s flammability, especially in powder or small-turnings form, can punish the careless with flare-ups. Fire risks get amplified as reactions scale up or as vapors concentrate in closed rooms, and the combination of magnesium with strong acids or oxidizers demands immediate respect. Protective gear and good air circulation make for a safer lab, and keeping water away from magnesium-clogged glassware keeps things from getting out of hand. Researchers can’t overlook the importance of training and clear safety protocols in any operation involving magnesium’s reactive touch.

How Magnesium Fuels Innovation and New Applications

Magnesium’s reach extends well beyond academic curiosity. Pharmaceutical chemists routinely use Grignard-derived reagents for new drug scaffolds, especially for compounds impractical by other means. Materials science branches out with magnesium-based synthesis for polymers, coatings, and even new battery chemistries. The ability to form carbon-carbon bonds reliably keeps magnesium relevant across fields: from producing flavors and fragrances to supplying starting points for agrochemical work. Every year, more scientists expand applications by introducing bioactive groups or using non-traditional solvents, running reactions at scale, and feeding data into the drive for ever more efficient and selective synthesis. Looking back at finished research, I can see how the direct confidence in handling magnesium bred opportunities for creative risk-taking in targets that seemed impossible just a generation ago.

Research, Development, and the Push Toward Greener Chemistry

Industries care about more than yields or conversion factors—environmental stewardship weighs on every synthetic protocol. Green chemistry advocates want less waste and safer reaction conditions, so ongoing studies target methods to use milder activation, less hazardous solvents, and recyclable magnesium sources. Researchers refine protocols for low-temperature operation or solvent recycling. Beyond industry, academic labs seek to demystify the variability in magnesium batches, aiming for standardized material that produces consistent results. Modern techniques like surface analysis, electron microscopy, and advanced spectroscopy map the fine details of reactivity and let people design smarter, cleaner processes. Fresh directions keep emerging: microwave-activated reactions, better in-line monitoring, and efforts to recover and reuse the metal from industrial waste streams.

Toxicity, Health, and the Undiscussed Risks

Magnesium doesn’t rank high on toxicity compared to the reactive chemicals it encounters in synthesis, and the human body actually needs it in small amounts. Working with the metal itself rarely poses chronic health risks outside the dangers of fire or inhalation of fine dust. The bigger story lies in how magnesium interacts with solvents, halides, and organic byproducts, some of which pose real health hazards. Proper ventilation, careful disposal, and protective equipment remain non-negotiable in any well-run lab. Safety data continues to accumulate, pointing out that acute exposure to reactive forms or combustion products brings respiratory concerns and irritation, especially for technicians and chemists managing batch-scale operations. Agencies tracking workplace safety keep magnesium on their radar as new data emerges from ever-evolving work practices.

Onward: Where Magnesium’s Story Might Lead

Looking ahead, the story of magnesium in chemical synthesis keeps on growing. Demand for more sustainable materials, coupled with advanced machinery and better process control, could make classic reactions cleaner and more accessible. Startups competing in pharmaceutical and materials innovation will rely on finely tuned magnesium protocols to reach new molecular space or to scale promising drugs from the bench to the plant. The continuing trend toward automation and digitized research—e-labs, machine learning-guided optimization—promises more reliable handling and fewer surprises from one batch to another. As attention turns to global resource management, magnesium’s abundance and low cost lend practical muscle to its future prospects, particularly in countries invested in expanding research infrastructure. In every corner of the chemical world, magnesium keeps opening doors for anyone meeting it with curiosity, respect, and a willingness to try just one more prep.




What purity of magnesium is required for Grignard reactions?

Tackling Purity in the Lab

Any chemist who has prepped a Grignard reagent knows the drill—load the flask with magnesium, drip in the alkyl halide, wait for the fizz and cloud. Sometimes it works, sometimes you’re left staring at absolutely nothing. Fresh magnesium shines bright, but not all that glitters is worth using. Quality matters, and it’s the difference between a bang and a fizzle.

Practical Purity Standards

Grignard reactions demand magnesium that’s at least 99% pure. Magnesium ribbon or turnings bought from reputable chemical suppliers fall right around this number—high enough to keep side reactions from spoiling the party, but not so expensive that you’re blowing the semester’s budget. Lab veterans usually grab the 99% or 99.5% stuff, since trace metals and oxide impurities less than 1% won’t stall most standard reactions.

Experience in the lab sometimes reveals trouble even with so-called high-purity magnesium. Air and moisture attack magnesium turnings long before they hit the reaction flask. Even trace amounts of magnesium oxide or hydroxide can coat the metal, stopping activation cold. The real trick comes down to prepping the surface, not just reading numbers on a bottle.

Why Impurities Matter More Than Percentages

A few tenths of a percent impurity won’t usually wreck a Grignard reaction, but certain contaminants hit hard. Iron, copper, aluminum, and even silicon can poison the sensitive reaction. I’ve seen batches of floor sweepings sold as "magnesium powder" barely bubble in ether. Iron filings sneak in from cheap production, and those spell disaster for the formation of the organomagnesium bond. Even if the label claims 98% magnesium, what matters is what that other 2% holds.

Fussy reactions—stubborn halides, extra-demanding syntheses—sometimes need a boost. That’s where the practice of “activating” magnesium pays off. A quick bath in dilute acid, an iodine crystal, or even a splash of 1,2-dibromoethane scrubs the oxide layer right off and gets things humming. Many chemists keep a box of these tricks handy because purity alone never tells the whole story.

Solutions that Work in Real Labs

College teaching labs often go through bottles labeled simply “magnesium ribbon,” trusting students to use sandpaper or acid to clean the metal before use. In industry, standard operating procedures spell out acceptable impurity levels—usually under 0.5% for reactive metals. Some fields, especially pharmaceutical synthesis, order lots tested for common poisons like lead and arsenic, since tiny quantities can ruin yields or contaminate drugs.

If the goal is just to make a student’s first phenylmagnesium bromide, the hardware-store grade won’t cut it. Reliable results come from sourcing reliable magnesium—and keeping it dry, sealed, and shiny. Years in the lab have shown that cutting a fresh surface or pre-washing with acid saves seemingly “dead” magnesium. Sharing these tricks lets others skip the frustration of waiting all afternoon for reaction that never comes.

Magnesium purity deserves as much attention as the choice of solvents and glassware. Without enough care, even fancy new reagents and perfect technique won't rescue an uncooperative reaction. Good chemistry stems from good preparation—and for Grignard work, magnesium purity sits right at the center of a successful experiment.

How should magnesium be stored to maintain its reactivity for Grignard reactions?

Why Magnesium Storage Matters for Chemists

Magnesium makes Grignard reagents possible. Without it, the entire process runs into trouble before it begins. If magnesium gets lazy, covered in a coat of oxide, or reacts with stray moisture, labs find themselves facing frustration, not breakthrough chemistry. I remember standing in a teaching lab, trying to coax an uncooperative gray ribbon to life, watching students stir and wait as nothing much happened. Those lessons stuck with me—missteps in storage waste time, material, and patience. Each failed reaction serves as a reminder: keeping magnesium fresh matters a lot more than a casual observer might think.

Magnesium’s Restless Chemistry

You can’t treat magnesium like iron nails on a shelf. Pure magnesium has energy to burn—literally. But once it meets water vapor or air, it quickly develops a stubborn oxide shell. Inside, you still have reactive metal, but getting there becomes trickier every day it sits exposed. Over time, taps or cuts become less effective, and sometimes nothing short of sandpaper gets through. If a batch of Grignard never gets going, odds are high an old layer of oxide is to blame.

The Realities of Moisture and Oxidation

In regular lab air, even trace humidity sneaks in to create trouble. Some people believe stocking magnesium in sealed bottles is enough, but air left behind in the container can still do its quiet damage bit by bit. Evidence rolls in from failed syntheses and the need for repeated activation steps like washing with acid or scraping surfaces. I’ve pulled out so-called “fresh” turnings only to find the familiar dusty gray that means lost productivity.

Simple Storage Tips from Practice

Sealing magnesium in a dry, airtight container works better than most alternatives. Screwing on caps right after weighing might look obsessive to outsiders, but anyone who’s spent time prepping Grignards knows it pays off. Glass or metal containers with tight seals give moisture no invitation. Adding a few silica gel packets inside the bottle keeps humidity at bay, especially in areas with sticky summers or wet winters. For labs with argon or nitrogen on tap, flushing the headspace and keeping things under inert gas basically freezes magnesium’s age. In my own work, I’ve seen containers handled this way deliver quick, hot reactions months after purchase, while dusty, open jars seem cursed.

Bulk Storage and Long-Term Considerations

Stockrooms often keep kilograms of magnesium ribbon or granules. Placing the main supply in a moisture-controlled cabinet—desiccators filled with calcium chloride or silica—protects the bulk material, while smaller portions can travel to working labs as needed. Some folk keep tools nearby for scraping the outer layer just in case, but with careful handling, it’s surprising how long magnesium can stay bright and ready.

What Works in the Real World

Textbook explanations sometimes miss the quiet reality of daily storage habits. Perfect inert atmospheres aren’t always possible, but even simple steps—air-tight lids, drying agents, and not leaving caps off—go a long way. Skipping those steps brings frustration and disappointment when a Grignard runs cold. The next time a colleague wonders why reactions come easy for some but stall for others, chances are the answer hides with how they treat their magnesium. Secure storage brings chemistry to life; neglect just brings wasted afternoons. A little extra effort on the shelf saves headaches on the bench.

Can magnesium turnings or powder be used interchangeably for Grignard reactions?

Real Lab Experience Often Tells a Different Story

Ask any organic chemist working with Grignard reactions, and you’ll get an earful about the practical bits that textbooks gloss over. Magnesium, in all its glory, pops up as either turnings or powder for this classic reaction. Open a catalog, and it might look like a choice with no consequences. But stirring a sluggish reaction for hours or breathing in that nasty solvent sting changes your perspective.

Launching the Grignard: Not Just a Matter of Magnesium

Preparation for a Grignard isn’t just mixing ingredients like cake batter. The struggle usually starts with the magnesium’s surface. Powdered magnesium comes with a much higher surface area. More surface means more sites for the alkyl or aryl halide to react. Turnings look duller and chunkier, packing far less reactive area. In a real lab, trying to kick off a Grignard with turnings can feel like urging a stubborn mule; sometimes the reaction just won’t start or fizzles into nothing.

Of course, too reactive isn’t always a blessing. Magnesium powder, especially in dry conditions, can react faster than new students expect, sometimes leading to runaway frothing or even sparks. Powder can also oxidize quicker in air, building up a stubborn oxide layer that’s more trouble than magnesium’s supposed to be worth. Folks often need to add a dash of iodine or a drop of dibromoethane to strip this oxidation and nudge the stubborn metal. Not every beginner expects the element itself to need “activation,” but that’s what gets Grignard rolling.

Safety in Practice

People who handle gram-scale reactions often find the difference matters less. Once you move up to bigger batches, powder brings a fire hazard that gets real attention from safety officers—not just a line in an MSDS. Spilled powder wafts into the air, ends up in dust, and with the right spark, metal powders can ignite. Turnings stick together, drop into flasks neatly, and rarely go airborne. If your lab values clean benches and quiet days, turnings usually get the nod for big reactions.

Cost and Supply: Everyday Realities

Labs that run lots of Grignard chemistry sometimes decide on form based on price or available stock. Companies charge more for finely divided powder. Sometimes, only turnings land on the loading dock, and the chemist has to work a little harder to get the reaction going. Tricks like grinding up turnings or stirring in a bit of sand come into play, all drawn from years of trial and error. I remember resorting to a mortar and pestle more than once after discovering the turnings sat on the shelf a bit too long.

What Actually Works Best

I’ve watched students try to fudge their way through a stubborn Grignard using whatever form of magnesium was lying around. The lucky ones got a quick reaction, while others spent hours adjusting temperature or scraping at the stubborn surface. People with experience know magnesium powder usually makes life easier, especially for tricky substrates or tiny batches. Yet, for safety, storage, and cost, the humble turnings serve just as well if you’re willing to wait or coax them along. Choice isn’t just about what’s “best” on paper; it’s driven by what you have, the scale you work on, and whether you value speed or caution.

Practical Solutions for Grignard Success

Success in Grignard chemistry comes from a mix of good planning and a few well-worn tricks. Store magnesium in airtight bottles to cut down on oxidation. Pre-activate turnings with a quick wash in dilute acid, then rinse and dry before use so stubborn oxide gets out of the way. Start small reactions with powder if you can, but reach for turnings when safety demands it or when you’re working bigger than a few grams. A dash of iodine or dibromoethane often wakes up lazy magnesium surfaces, too. What matters most is understanding your own reaction setup—knowing which tradeoffs you can accept beats following a rulebook every time.

What is the best method to activate magnesium for Grignard reagent preparation?

A Hands-On Perspective from the Lab Bench

Anyone who has spent time with organometallics knows one common headache: getting magnesium to kick off a lively Grignard reaction. Magnesium can be stubborn, especially if it’s oxidized or comes from a batch with a passivated surface. Many researchers run into trouble with this step, leading to wasted time, low yields, and questions about what’s gone wrong. Here’s my take after years handling magnesium in all sorts of labs, from teaching undergraduate organic chemistry to cooking up oddball substrates for graduate projects.

The Role of Surface in Magnesium Reactivity

Active magnesium means clean magnesium. A bright, almost silvery surface signals it’s ready for chemistry, but more often it looks dull or gray from surface oxidation. This layer creates a barrier—not enough electrons leaking out where you need them. Relying on untreated turnings or powder sometimes brings disappointment.

Scratching and Crushing: Old-School, Reliable Methods

Many chemists reach for a mortar and pestle before even setting up the flask. Grinding magnesium or scratching it with a glass rod in the reaction solvent exposes more fresh metal. It’s messy, it’s simple, and it works because magnesium’s reactivity kicks in best on a naked surface. I’ve found that even just breaking up the turnings inside the setup with a strong spatula or a magnetic stir bar helps more than most fancy tricks.

A Dash of Iodine or Dibromoethane: Not Just Tradition

If scratching doesn’t do the trick, a pinch of iodine or a drop of 1,2-dibromoethane almost always coaxes the magnesium to life. Both open up that oxide layer through chemical activation. Iodine reacts, creating magnesium iodide and cleaning the surface. Once the Grignard reaction starts, it usually takes off, and the color from iodine fades out, showing activation is working. In tough cases, a second drop can tip the balance. Dibromoethane acts similarly, with the benefit of leaving behind far less visible residue. In crowded reactions or sensitive analytical work, dibromoethane feels preferable—less stray color, fewer questions about leftover byproducts.

Heat: Helpful, but Not a Cure-All

Warming up the solvent sometimes moves things along, but too much heat can turn the whole setup volatile—literally. Ether solvents start getting dangerous when they get too warm. Good stirring and direct attention during heating matter more than cranking up the temperature. If nothing happens after iodine or dibromoethane, odds are the magnesium’s the issue: too oxidized, old, or from a batch that never behaves right.

Fresh Magnesium: Not a Luxury, but a Necessity

A lot of reactions take off just by switching to a new bottle. Sometimes cheaper bulk magnesium includes a thick oxide layer from sitting on the shelf. When preparing Grignard reagents in teaching labs, I’d always check the stock—nothing ruins demonstrations faster than dead magnesium. In my own research, ordering small, fresh lots gave more consistent results. It beats endlessly grinding or using extra additives that might cause post-reaction headaches.

Wrapping Up: Simplicity Wins

Getting magnesium to do its job rests on keeping surfaces clean and accessible. Physical methods, a little chemical help, and paying attention to the source of your metal pay off more than high-tech tricks or expensive additives. Small changes—a grind here, a dash of iodine there—make the difference between stalled out and full reaction. Most of us find the old ways still hold up.

How should leftover magnesium from Grignard reactions be safely disposed of?

Managing Magnesium Waste in Chemistry Labs

Every synthetic chemist knows the power and frustration behind a Grignard reaction. Magnesium turnings or powder help fuel much of modern organic chemistry, but the leftover metal always sits at the bottom of a beaker looking harmless and silvery, waiting for someone to deal with the mess. Safety cannot be ignored here—cleanup decisions ripple out to lab mates, future students, and the sustainability record of an entire department.

Scrap Magnesium Isn’t Harmless

Magnesium loves to react, which makes it perfect for Grignard chemistry and dangerous in the trash. Tossing raw turnings in the bin is asking for trouble. The moment they hit water, even from damp air or cleaning rags, there’s a risk of heat, sparks, or fire. A few years ago in my own lab, a rash disposal tossed Mg in the wrong waste can—smoky drama and fire department visits make lessons stick.

Quenching Magnesium Waste Step by Step

The responsible route starts by destroying any leftover reactivity. Quenching stands as the word chemists use for rendering the stuff safe. Rushing into things with water spells disaster. Slow addition of alcohol like isopropanol or ethanol—never the cheap stuff straight from the jug—tames the reaction. Shield your face and hands, keep glassware on ice, and add the alcohol dropwise. Hydrogen will bubble off, but the reaction shouldn’t overheat or splatter. Only after the fizzing calms down do you think about following up with a water rinse, always with caution.

After quenching, the bulk of the magnesium now rests as an alcoholate or hydroxide sludge. Chemists should transfer this goopy material into a labeled waste solvent container. Most university or industrial chem-waste haulers know what to do next. The spent magnesium won’t be sparking up on a truck, and environmental risk drops way down.

Legal and Environmental Gaps

EPA and local environmental agencies draw hard lines around heavy metals. Magnesium stands less toxic than lead or chromium, but dumping metal scrap in regular drains or trash crosses those lines. Even small amounts add up across hundreds or thousands of reactions, and a good chemist ought to take that big picture seriously. Fact: magnesium can disrupt natural aquatic systems when it leaves the lab unchecked, so keeping it bottled up, tagged, and tracked supports both safety and science’s social license.

Culture of Safety Starts with Training

Disposing of leftover magnesium turns into a teaching moment for all labs, whether in academia or industry. Encourage open reporting of near-misses with reactive waste. Write protocols with specifics on how much alcohol per gram of metal, then post them at every bench. Senior researchers can walk through the first couple of cleanups with new hires. Nothing beats direct experience for drilling safe habits.

Moving Toward Greener Choices

Some labs now swap out magnesium for less reactive metals where possible or design reactions where the metal can be filtered out and recycled rather than destroyed. Still, Grignard chemistry isn’t fading away anytime soon—so diligent quenching and smart waste handling remain everyone’s responsibility.

Magnesium (for Grignard Reactions)
Names
Preferred IUPAC name Magnesium
Other names Magnesium turnings
Magnesium powder
Pronunciation /mæɡˈniːziəm/
Identifiers
CAS Number 7439-95-4
Beilstein Reference 13611
ChEBI CHEBI:25107
ChEMBL CHEMBL1208759
ChemSpider 14107
DrugBank DB14096
EC Number 231-104-6
Gmelin Reference Mg 11
KEGG C00034
MeSH D008279
PubChem CID 888
RTECS number OM2100000
UNII 7QB9PV8ED7
UN number UN1418
Properties
Chemical formula Mg
Molar mass 24.305 g/mol
Appearance A fine, silver-grey powder or turnings.
Odor Odorless
Density 1.74 g/mL at 25 °C
Solubility in water insoluble
log P -0.96
Vapor pressure Negligible
Acidity (pKa) 45
Basicity (pKb) 5.70
Magnetic susceptibility (χ) −13.0×10⁻⁶ cm³/mol
Refractive index (nD) 1.425
Dipole moment 0 D
Thermochemistry
Std molar entropy (S⦵298) 32.7 J/(mol·K)
Std enthalpy of formation (ΔfH⦵298) 0 kJ mol⁻¹
Std enthalpy of combustion (ΔcH⦵298) “-601.6 kJ mol⁻¹”
Pharmacology
ATC code V04CP01
Hazards
GHS labelling GHS07, GHS08
Pictograms GHS02, GHS07
Signal word Warning
Hazard statements H228, H261
Precautionary statements P210, P222, P231+P232, P280, P370+P378, P404, P501
NFPA 704 (fire diamond) 1-3-2-W
Autoignition temperature 473 °C (883 °F)
Explosive limits Lower: 0.03 oz/ft³; Upper: 0.3 oz/ft³
Lethal dose or concentration LD50 orally in rat: 230 mg/kg
LD50 (median dose) LD50 (median dose): Oral-rat LD50: 230 mg/kg
NIOSH MG30000
PEL (Permissible) 10 mg/m3
REL (Recommended) 50 mg/m³
IDLH (Immediate danger) 5,000 mg/m3
Related compounds
Related compounds Calcium (for Grignard Reactions)
Magnesium Turnings
Sodium (for Synthesis)
Lithium (for Synthesis)
Zinc (for Organic Synthesis)