What Is The Aphorism Used By Chemists To Describe Polarity
What Is the Aphorism Chemists Use to Describe Polarity?
You've probably seen it in a textbook, scribbled on a whiteboard, or muttered in a lecture hall without quite catching what it means. Because of that, " Three words. In practice, "Like dissolves like. And yet they do an enormous amount of work in chemistry.
The phrase sounds almost too simple to be useful, but it's one of those ideas that quietly explains a huge amount of everyday lab behavior — why oil and water separate, why some solvents wipe grease off a surface while others leave it untouched, and why certain crystals dissolve in acetone but not in ethanol.
Let's dig into what this little rule actually means, where it comes from, and why it still matters.
What "Like Dissolves Like" Actually Means
The saying refers to polarity — a property of molecules that describes how electrical charge is distributed across their structure. In simple terms, some molecules have regions that are slightly more positive and regions that are slightly more negative. Others are more electrically balanced, with charge spread out evenly.
Chemists call the first group polar molecules and the second group nonpolar molecules.
The aphorism says: polar solvents dissolve polar solutes, and nonpolar solvents dissolve nonpolar solutes. Mix the two, and they don't play nicely.
Water is the classic polar solvent. In real terms, salt (sodium chloride) is a polar solute. But water pulls the sodium and chloride ions apart and surrounds them with its own charged ends — that's why salt disappears in a glass of water. But add olive oil, which is nonpolar, and water ignores it. The two form separate layers because there's no electrical reason for them to mix.
The Origin of the Phrase
Nobody really "invented" the saying in a single moment. And it's a distillation of observations that chemists made over centuries. By the 19th century, people working with solvents had noticed the pattern empirically: certain liquids dissolved certain solids and not others, and the pattern seemed tied to whether the substances shared a similar character.
The modern phrasing — "like dissolves like" — is credited loosely to mid-20th century chemistry teaching, where instructors needed a quick, memorable way to convey the underlying principle to students. It's not a formal law the way thermodynamics has laws, and it doesn't come with equations. It's a heuristic, which is a fancy way of saying "a useful rule of thumb.
Polarity Isn't Just Black and White
Here's where a lot of people get tripped up. "Polar" and "nonpolar" aren't strict categories with a hard wall between them. Molecules exist on a spectrum.
Take ethanol. So ethanol is somewhere in the middle — partially polar, partially nonpolar. It has a polar hydroxyl group (the –OH end) and a nonpolar hydrocarbon tail. Consider this: that's why it can dissolve a wider range of substances than pure water can. It bridges the gap.
A molecule's polarity is usually described in terms of its dipole moment — a measurement of how separated the positive and negative charges are within the molecule. A higher dipole moment means a more polar molecule. A dipole moment of zero means the charges are perfectly balanced and the molecule is nonpolar.
The shape of a molecule matters too. Carbon dioxide, for instance, has polar bonds (oxygen is more electronegative than carbon), but the molecule is linear, so the pulls cancel out. The result: CO₂ is nonpolar overall, even though its individual bonds are not.
Why This Rule Matters So Much
It sounds like a textbook detail. In practice, it's the thing standing between a successful experiment and a cloudy, useless mess.
In the Lab
If you're trying to recrystallize a compound — a common purification technique — you need to choose a solvent in which your target compound is soluble when hot but not when cold. Get the polarity wrong, and either nothing dissolves, or everything stays dissolved and you walk away with nothing.
Liquid-liquid extraction works on the same principle. Polar compounds migrate into the polar layer. On the flip side, the two layers separate, and you draw them off separately. You pick two immiscible solvents (usually water and an organic one like diethyl ether or hexane) and shake your mixture with them. Nonpolar compounds move into the nonpolar layer. Without the polarity mismatch, this wouldn't work at all.
In Industry and Drug Design
Pharmaceutical chemists obsess over polarity. And a drug molecule has to dissolve in your bloodstream (a polar environment) to get where it needs to go, but it also has to cross cell membranes (which are largely nonpolar in their interior). That's why drug design involves so much fiddling with a molecule's polar and nonpolar regions — too polar and it can't get inside cells, too nonpolar and it can't travel through the watery parts of your body.
This is also why you'll see a "logP" value on chemical safety data sheets. It's a measure of how a substance partitions between a nonpolar solvent (octanol) and water. And higher logP means more nonpolar, lower logP means more polar. Formulators use it to predict how a chemical will behave in mixtures, in the environment, and in biological systems.
In Everyday Life
The same rule explains why dish soap works. Practically speaking, dish soap molecules have a polar head and a long nonpolar tail — a structure called a surfactant. In practice, grease is nonpolar. In practice, the tails grab onto the grease, the heads stay attached to the water, and the whole mess washes down the drain. Water alone can't lift it off a plate. The soap acts as a translator between two substances that otherwise wouldn't mix.
Dry cleaning uses a nonpolar solvent (traditionally perchloroethylene, sometimes other hydrocarbons now) to clean fabrics that water would damage or fail to penetrate. The nonpolar solvent dissolves body oils, sweat residue, and grease-based stains that water would just smear around.
Common Misconceptions About Polarity
A few things trip people up regularly.
"Polar molecules are charged." Not quite. Polarity refers to an uneven distribution* of charge within an otherwise neutral molecule. A polar molecule has partial charges (often written with a δ+ and δ−), not full ionic charges. Full charges would make it an ion, which is a different beast.
"If two liquids are both polar, they mix." Not always. Some polar solvents are immiscible with each other — water and certain alcohols of longer chain length, for example, can show partial miscibility. The molecular geometry and the strength of the intermolecular forces (hydrogen bonding, dipole-dipole interactions, van der Waals forces) all play a role.
"Polarity explains everything about solubility." It explains a lot, but not everything. Temperature, pressure (for gases), crystal lattice energy, and molecular size all influence whether something dissolves. Polarity is the headline, not the whole story.
For more on this topic, read our article on alaskan king crab is one of the most prized shellfish or check out write the complement of each of the following angles.
Practical Tips for Applying the Rule
When you're staring at an unknown solute and trying to pick a solvent, here's a quick mental checklist:
- Is your solute ionic or highly polar? Start with water, methanol, or ethanol.
- Is your solute a hydrocarbon, oil, or fat? Try hexane, toluene, or dichloromethane.
- Somewhere in between? Ethanol, isopropanol, or acetone often works because they straddle the polarity line.
- Still stuck? Mix two solvents in different ratios. A 50/50 mix of a polar and nonpolar solvent can be tuned to dissolve a surprising number of compounds. This is called a solvent system and it's a standard move in chromatography.
A handy mental image: think of polarity as a kind of social compatibility. Which means trying to mix the two is like forcing two people with nothing in common to share a small room. Think about it: nonpolar molecules are loners, content in their own even, electrically quiet world. Consider this: polar molecules want to be around other polar molecules because they can share electrical attractions. They might tolerate it, but they're not going to become friends.
FAQ
Is "like dissolves like" a real law? Not in the strict sense. It's a heuristic — a practical rule that holds true in most cases but has exceptions. It's derived from thermodynamics, specifically from the idea that mixing is favored when intermolecular forces between solute and solvent are similar in strength and type.
What's the opposite of "like dissolves like"? There's no single famous opposite phrase, but chemists sometimes refer to substances that don't mix as immiscible and the phenomenon as phase separation. Oil and water are the textbook example.
Can two nonpolar substances fail to dissolve in each other? Rarely, but yes. Polarity is one factor, but molecular size, shape, and the strength of van der Waals interactions also matter. Two very different nonpolar molecules might still not form a homogeneous
Phase behavior of non‑polar mixtures
Two non‑polar liquids can still refuse to blend if their molecular volumes or shapes are too mismatched. Here's one way to look at it: the long, linear chain of n‑hexane* (C₆H₁₄) sits comfortably alongside other straight‑chain alkanes, but a bulky, rigid cyclo‑alkane such as cyclooctane* may pack poorly with a small, spherical molecule like neopentane* (C(CH₃)₄). The resulting van der Waals attractions are weak in both pure substances, yet the energy gain from mixing is often too small to overcome the entropic penalty of bringing two unlike structures together. In practice, this shows up as a partial miscibility gap—the two liquids will separate into two layers, even though each is non‑polar.
A useful quantitative way to predict such deviations is the Hansen solubility parameter (HSP) system. Each solvent (or solute) is characterized by three components:
| Component | Symbol | What it measures |
|---|---|---|
| Dispersion forces | δ_D | van der Waals interactions |
| Polar interactions | δ_P | Dipole‑dipole, induced‑dipole forces |
| Hydrogen bonding | δ_H | Specific H‑bond donor/acceptor ability |
Two substances are likely to be miscible when their HSP vectors are close in three‑dimensional space. In practice, , a tiny molecule with weak dispersion versus a large aromatic with strong π‑π interactions) can push them into separate phases. In practice, g. HSP calculators and software packages (e.In real terms, even if both are non‑polar, a large disparity in δ_D (e. g., HSPiP) let chemists run “what‑if” scenarios quickly, turning the rule‑of‑thumb “like dissolves like” into a numeric estimate.
Beyond polarity: temperature, pressure, and concentration
- Temperature – For most solids dissolving in liquids, solubility rises with temperature because the lattice energy of the solid is outweighed by increased kinetic energy and entropy. Even so, some exothermic dissolution processes (e.g., calcium sulfate in water) actually become less soluble as temperature climbs. The sign of the enthalpy of solution (ΔH_sol) decides the direction.
- Pressure – Gases obey Henry’s law: solubility ∝ pressure. A non‑polar gas like CO₂ dissolves better in a non‑polar solvent under high pressure—a principle exploited in supercritical CO₂ extraction.
- Concentration & activity coefficients – In real solutions, the activity coefficient (γ) deviates from 1 when solute–solvent interactions differ markedly from solute–solute or solvent–solvent interactions. A γ > 1 indicates “antagonistic” forces (
antagonistic” forces that make the solute “want” to escape the solution, effectively raising its escaping tendency above the ideal prediction. Conversely, γ < 1 signals favorable solute–solvent interactions (e.g., strong hydrogen bonding or charge-transfer complexes) that stabilize the mixture. These deviations are the thermodynamic root of phenomena such as azeotrope formation, where the vapor and liquid phases share the same composition, and liquid–liquid equilibrium (LLE), where a single homogeneous phase splits into two coexisting layers of different composition. In both cases, the simple “like dissolves like” heuristic fails because the balance of enthalpic and entropic contributions creates non‑linear composition dependencies that cannot be captured by polarity alone.
Modern process design therefore relies on thermodynamic models—UNIFAC, COSMO‑RS, NRTL, or electrolyte extensions of these frameworks—to translate molecular structure into activity coefficients across the entire composition range. These tools allow engineers to predict whether a solvent will form a single phase with a solute at process conditions, whether an azeotrope will limit distillation purity, or whether a temperature swing can break a miscibility gap. Coupled with Hansen solubility parameters for initial screening, they turn solubility from a qualitative guideline into a quantitative design variable.
Conclusion
Solubility is ultimately a contest between intermolecular forces and thermal disorder. Polarity, hydrogen bonding, and dispersion interactions set the baseline affinity between molecules, but molecular size, shape, and flexibility modulate how efficiently those forces can be realized in the condensed phase. Temperature and pressure shift the balance by altering kinetic energy and volumetric constraints, while concentration-dependent activity coefficients reveal the collective, non‑ideal behavior that gives rise to azeotropes, miscibility gaps, and complex phase diagrams. By combining intuitive concepts—“like dissolves like,” Hansen’s three‑dimensional solubility space—with rigorous thermodynamic models, chemists and engineers can handle this multidimensional landscape, designing separations, formulations, and reactions that work reliably in the real world.
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