Surface tension

For the short story, see Surface Tension (short story)

Continuum mechanics

Conservation of mass Conservation of momentum Navier–Stokes equations
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Surface tension is a property of the surface of a liquid that causes it to behave as an elastic sheet. Surface Tension is a Science fiction Short story by James Blish originally published in 1952 Continuum mechanics is a branch of Mechanics that deals with the analysis of the Kinematics and mechanical behavior of materials modeled as a continuum e The law of conservation of mass/matter, also known as law of mass/matter conservation (or the Lomonosov - Lavoisier law says that the Mass of In Classical mechanics, momentum ( pl momenta SI unit kg · m/s, or equivalently N · s) is the product The Navier–Stokes equations, named after Claude-Louis Navier and George Gabriel Stokes, describe the motion of viscous Fluid substances such Liquid is one of the principal States of matter. A liquid is a Fluid that has the particles loose and can freely form a distinct surface at the boundaries of A material is said to be elastic if it deforms under stress (e It allows insects, such as the water strider (pond skater, UK), to walk on water. Insects ( Class Insecta) are a major group of Arthropods and the most diverse group of Animals on the Earth with over a million described The family Gerridae contains insects commonly known as water striders, water bugs, magic bugs, pond skaters, skaters, skimmers The United Kingdom of Great Britain and Northern Ireland, commonly known as the United Kingdom, the UK or Britain,is a Sovereign state located Water is a common Chemical substance that is essential for the survival of all known forms of Life. It allows small objects, even metal ones such as needles, razor blades, or foil fragments, to float on the surface of water, and it is the cause of capillary action. Capillary action, capillarity, capillary motion, or wicking is the ability of a substance to draw another substance into it

The physical and chemical behavior of liquids cannot be understood without taking surface tension into account. It governs the shape that small masses of liquid can assume and the degree of contact a liquid can make with another substance.

Applying Newtonian physics to the forces that arise due to surface tension accurately predicts many liquid behaviors that are so commonplace that most people take them for granted. Classical mechanics is used for describing the motion of Macroscopic objects from Projectiles to parts of Machinery, as well as Astronomical objects Applying thermodynamics to those same forces further predicts other more subtle liquid behaviors. In Physics, thermodynamics (from the Greek θερμη therme meaning " Heat " and δυναμις dynamis meaning "

Cause

Diagram of the forces on a molecule of liquid.

Surface tension is caused by the attraction between the liquid's molecules by various intermolecular forces. In Chemistry, a molecule is defined as a sufficiently stable electrically neutral group of at least two Atoms in a definite arrangement held together by In Physics, Chemistry, and Biology, intermolecular forces are forces that act between stable Molecules or between functional groups of In the bulk of the liquid, each molecule is pulled equally in all directions by neighbouring liquid molecules, resulting in a net force of zero. At the surface of the liquid, the molecules are pulled inwards by other molecules deeper inside the liquid and are not attracted as intensely by the molecules in the neighbouring medium (be it vacuum, air or another liquid). Therefore, all of the molecules at the surface are subject to an inward force of molecular attraction which is balanced only by the liquid's resistance to compression, meaning there is no net inward force. However, there is a driving force to diminish the surface area, and in this respect a liquid surface resembles a stretched elastic membrane. Thus the liquid squeezes itself together until it has the locally lowest surface area possible.

Another way to view it is that a molecule in contact with a neighbor is in a lower state of energy than if it wasn't in contact with a neighbour. The interior molecules all have as many neighbours as they can possibly have. But the boundary molecules have fewer neighbours than interior molecules and are therefore in a higher state of energy. For the liquid to minimize its energy state, it must minimize its number of boundary molecules and must therefore minimize its surface area. ^[1]^[2]

As a result of surface area minimization, a surface will assume the smoothest shape it can (mathematical proof that "smooth" shapes minimize surface area relies on use of the Euler–Lagrange equation). In Calculus of variations, the Euler–Lagrange equation, or Lagrange's equation is a Differential equation whose solutions are the functions Since any curvature in the surface shape results in greater area, a higher energy will also result. Consequently the surface will push back against any curvature in much the same way as a ball pushed uphill will push back to minimize its gravitational potential energy.

Effects in everyday life

Water beading on a leaf

Water dropping from a tap

Some examples of the effects of surface tension seen with ordinary water:

Beading of rain water on the surface of a waxed automobile. Water adheres weakly to wax and strongly to itself, so water clusters into drops. Surface tension gives them their near-spherical shape, because a sphere has the smallest possible surface area to volume ratio.

Formation of drops occurs when a mass of liquid is stretched. A drop or droplet is a small volume of Liquid, bounded completely or almost completely by Free surfaces Surface tension The animation shows water adhering to the faucet gaining mass until it is stretched to a point where the surface tension can no longer bind it to the faucet. It then separates and surface tension forms the drop into a sphere. If a stream of water were running from the faucet, the stream would break up into drops during its fall. Gravity stretches the stream, then surface tension pinches it into spheres. ^[3]

Flotation of objects denser than water occurs when the object is nonwettable and its weight is small enough to be born by the forces arising from surface tension. ^[2]

Separation of oil and water is caused by a tension in the surface between dissimilar liquids. This type of surface tension goes by the name "interface tension", but its physics are the same.

Tears of wine is the formation of drops and rivulets on the side of a glass containing an alcoholic beverage. The phenomenon called tears of wine is manifested as a ring of clear liquid near the top of a glass of Wine, from which droplets form and flow back into the wine Its cause is a complex interaction between the differing surface tensions of water and ethanol.

Surface tension is visible in other common phenomena, especially when certain substances, surfactants, are used to decrease it:

Soap bubbles have very large surface areas with very little bulk. Surfactants are wetting agents that lower the Surface tension of a liquid allowing easier spreading and lower the Interfacial tension between two liquids A soap bubble is a very thin film of Soap water that forms a Sphere with an iridescent Surface. Bubbles in pure water are unstable. The addition of surfactants, however, can have a stabilizing effect on the bubbles (see Marangoni effect). The Marangoni effect (sometimes also called the Gibbs-Marangoni effect) is the mass transfer on or in a liquid layer due to Surface tension differences Notice that surfactants actually reduce the surface tension of water by a factor of three or more.

Emulsions are a type of solution in which surface tension plays a role. An emulsion ( IPA: /ɪˈmʌlʃən/ is a mixture of two Immiscible (unblendable liquids Tiny fragments of oil suspended in pure water will spontaneously assemble themselves into much larger masses. But the presence of a surfactant provides a decrease in surface tension, which permits stability of minute droplets of oil in the bulk of water (or vice versa).

Basic physics

Two definitions

Diagram shows, in crossection, a needle floating on the surface of water. Its weight, , depresses the surface, and is balanced by the surface tension forces on either side, , which are each parallel to the water's surface at the points where it contacts the needle. Notice that the horizontal components of the two arrows point in opposite directions, so they cancel each other, but the vertical components point in the same direction and therefore add up to balance .

Diagram shows, in crossection, a needle floating on the surface of water. Its weight, $\scriptstyle f_w$ , depresses the surface, and is balanced by the surface tension forces on either side, $\scriptstyle f_s$ , which are each parallel to the water's surface at the points where it contacts the needle. Notice that the horizontal components of the two $\scriptstyle f_s$ arrows point in opposite directions, so they cancel each other, but the vertical components point in the same direction and therefore add up^[2] to balance $\scriptstyle f_w$ .

Surface tension, represented by the symbol σ, γ or T, is defined as the force along a line of unit length, where the force is parallel to the surface but perpendicular to the line. Sigma (upper case Σ, lower case σ; Greek Σιγμα lower case in word-final position ς) is the eighteenth letter of the Greek Gamma (uppercase &Gamma, lowercase γ Γάμμα is the third letter of the Greek alphabet. T is the twentieth letter in the modern Latin alphabet. Its name in English is spelled tee or occasionally te (tiː One way to picture this is to imagine a flat soap film bounded on one side by a taut thread of length, L. The thread will be pulled toward the interior of the film by a force equal to 2γL (the factor of 2 is because the soap film has two sides hence two surfaces). ^[4] Surface tension is therefore measured in forces per unit length. In Physics, a force is whatever can cause an object with Mass to Accelerate. Length is the long Dimension of any object The length of a thing is the distance between its ends its linear extent as measured from end to end Its SI unit is newton per metre but the cgs unit of dynes per cm is most commonly used. The newton (symbol N) is the SI derived unit of Force, named after Isaac Newton in recognition of his work on Classical The centimetre-gram-second system ( CGS) is a system of physical units. A centimetre ( American spelling: centimeter, symbol cm) is a unit of Length in the Metric system, equal to one hundredth ^[5] One dyn/cm corresponds to 0. 001 N/m.

An equivalent definition, one that is useful in thermodynamics, is work done per unit area. In Physics, thermodynamics (from the Greek θερμη therme meaning " Heat " and δυναμις dynamis meaning " In Physics, mechanical work is the amount of Energy transferred by a Force. As such, in order to increase the surface area of a mass of liquid by an amount, δA, a quantity of work, γδA, is needed. ^[4] This work is stored as potential energy. Consequently surface tension can be also measured in SI system as joules per metre² and in the cgs system as ergs per cm². The centimetre-gram-second system ( CGS) is a system of physical units. A centimetre ( American spelling: centimeter, symbol cm) is a unit of Length in the Metric system, equal to one hundredth Since mechanical systems try to find a state of minimum potential energy, a free droplet of liquid naturally assumes a spherical shape, which has the minimum surface area for a given volume.

The equivalence of measurement of energy per unit area to force per unit length can be proven by dimensional analysis. Dimensional analysis is a conceptual tool often applied in Physics, Chemistry, Engineering, Mathematics and Statistics to understand ^[4]

Water striders

Water striders using water surface tension when mating.

The photograph shows water striders standing on the surface of a pond. The family Gerridae contains insects commonly known as water striders, water bugs, magic bugs, pond skaters, skaters, skimmers It is clearly visible that their feet cause indentations in the water's surface. And it is intuitively evident that the surface with indentations has more surface area than a flat surface. If surface tension tends to minimize surface area, how is it that the water striders are increasing the surface area?

Recall that what nature really tries to minimize is potential energy. By increasing the surface area of the water, the water striders have increased the potential energy of that surface. But note also that the water striders' center of mass is lower than it would be if they were standing on a flat surface. So their potential energy is decreased. Indeed when you combine the two effects, the net potential energy is minimized. If the water striders depressed the surface any more, the increased surface energy would more than cancel the decreased energy of lowering the insects' center of mass. If they depressed the surface any less, their higher center of mass would more than cancel the reduction in surface energy. ^[6]

The photo of the water striders also illustrates the notion of surface tension being like having an elastic film over the surface of the liquid. In the surface depressions at their feet it is easy to see that the reaction of that imagined elastic film is exactly countering the weight of the insects.

Surface curvature and pressure

Surface tension forces acting on a tiny (differential) patch of surface. δθ_x and δθ_y indicate the amount of bend over the dimensions of the patch. Balancing the tension forces with pressure leads to the Young-Laplace equation

If no force acts normal to a tensioned surface, the surface must remain flat. In Physics, the Young&ndashLaplace equation is a Nonlinear Partial differential equation that describes the Capillary pressure difference sustained But if the pressure on one side of the surface differs from pressure on the other side, the pressure difference times surface area results in a normal force. In order for the surface tension forces to cancel the force due to pressure, the surface must be curved. The diagram shows how surface curvature of a tiny patch of surface leads to a net component of surface tension forces acting normal to the center of the patch. When all the forces are balanced, the resulting equation is known as the Young–Laplace equation:^[1]

$\Delta P\ =\ \gamma \left( \frac{1}{R_x} + \frac{1}{R_y} \right)$

where:

ΔP is the pressure difference. In Physics, the Young&ndashLaplace equation is a Nonlinear Partial differential equation that describes the Capillary pressure difference sustained
γ is surface tension.
R_x and R_y are radii of curvature in each of the axes that are parallel to the surface.

The quantity in parentheses on the right hand side is in fact (twice) the mean curvature of the surface (depending on normalisation). In Mathematics, the mean curvature H of a Surface S is an extrinsic measure of Curvature that comes from Differential

Solutions to this equation determine the shape of water drops, puddles, menisci, soap bubbles, and all other shapes determined by surface tension (such as the shape of the impressions that a water strider's feet make on the surface of a pond).

The table below shows how the internal pressure of a water droplet increases with decreasing radius. For not very small drops the effect is subtle, but the pressure difference becomes enormous when the drop sizes approach the molecular size.

ΔP for water drops of different radii at STP
Droplet radius	1 mm	0. In Physical sciences standard conditions for temperature and pressure are Standard sets of conditions for experimental measurements to allow comparisons to be made The Millimetre ( American spelling: millimeter, symbol mm) is a unit of Length in the Metric system, equal to 1 mm	1 μm	10 nm
ΔP (atm)	0. A micrometre ( American spelling: micrometer; symbol µm) is one millionth of a Metre, or equivalently one thousandth of a Millimetre A nanometre ( American spelling: nanometer, symbol nm) ( Greek: νάνος nanos dwarf; μετρώ metrό count) is a The Standard atmosphere is an international reference pressure defined as 101325 Pa and formerly used as unit of Pressure (symbol atm 0014	0. 0144	1. 436	143. 6

Liquid surface as a computer

Minimal surface

To find the shape of the minimal surface bounded by some arbitrary shaped frame using strictly mathematical means can be a daunting task. In Mathematics, a Minimal surface is a surface with a Mean curvature of zero Yet by fashioning the frame out of wire and dipping it in soap-solution, an approximately minimal surface (exact in the absence of gravity) will appear in the resulting soap-film within seconds. Without a single calculation, the soap-film arrives at a solution to a complex minimization equation on its own. ^[4]^[7]

The reason for this is that the pressure difference across a fluid interface is proportional to the mean curvature, as seen in the Young-Laplace equation. In Mathematics, the mean curvature H of a Surface S is an extrinsic measure of Curvature that comes from Differential In Physics, the Young&ndashLaplace equation is a Nonlinear Partial differential equation that describes the Capillary pressure difference sustained For an open soap film, the pressure difference is zero, hence the mean curvature is zero, and minimal surfaces have the property of zero mean curvature.

Contact angles

Since no liquid can exist in a perfect vacuum, the surface of any liquid is an interface between that liquid and some other medium. The top surface of a pond, for example, is an interface between the pond water and the air. Surface tension, then, is not a property of the liquid alone, but a property of the liquid's interface with another medium. If a liquid is in a container, then besides the liquid/air interface at its top surface, there is also an interface between the liquid and the walls of the container. The surface tension between the liquid and air is usually different (greater than) its surface tension with the walls of a container. And where the two surfaces meet, their geometry must be such that all forces balance. ^[1]^[4]

Forces at contact point shown for contact angle greater than 90° (left) and less than 90° (right)

Where the two surfaces meet, they form a contact angle, $\scriptstyle \theta$ , which is the angle the tangent to the surface makes with the solid surface. The contact angle is the Angle at which a Liquid / Vapor interface meets the solid surface The diagram to the right shows two examples. Tension forces are shown for the liquid-air interface, the liquid-solid interface, and the solid-air interface. The example on the left is where the difference between the liquid-solid and solid-air surface tension, $\scriptstyle \gamma_{\mathrm{ls}} - \gamma_{\mathrm{sa}}$ , is less than the liquid-air surface tension, $\scriptstyle \gamma_{\mathrm{la}}$ , but is nevertheless positive, that is

$\gamma_{\mathrm{la}}\ >\ \gamma_{\mathrm{ls}} - \gamma_{\mathrm{sa}}\ >\ 0$

In the diagram, both the vertical and horizontal forces must cancel exactly at the contact point. The horizontal component of $\scriptstyle f_\mathrm{la}$ is canceled by the adhesive force, $\scriptstyle f_\mathrm{A}$ . ^[4]

$f_\mathrm{A}\ =\ f_\mathrm{la} \sin \theta$

The more telling balance of forces, though, is in the vertical direction. The vertical component of $\scriptstyle f_\mathrm{la}$ must exactly cancel the force, $\scriptstyle f_\mathrm{ls}$ . ^[4]

$f_\mathrm{ls} - f_\mathrm{sa}\ =\ -f_\mathrm{la} \cos \theta$

Liquid

Solid

Contact angle

water

soda-lime glass

lead glass

fused quartz

0°

paraffin wax

107°

silver

90°

methyl iodide

soda-lime glass

29°

lead glass

30°

fused quartz

33°

mercury

soda-lime glass

140°

Some liquid-solid contact angles^[4]

Since the forces are in direct proportion to their respective surface tensions, we also have:^[1]

$\gamma_\mathrm{ls} - \gamma_\mathrm{sa}\ =\ -\gamma_\mathrm{la} \cos \theta$

where

$\scriptstyle \gamma_\mathrm{ls}$ is the liquid-solid surface tension,
$\scriptstyle \gamma_\mathrm{la}$ is the liquid-air surface tension,
$\scriptstyle \gamma_\mathrm{sa}$ is the solid-air surface tension,
$\scriptstyle \theta$ is the contact angle, where a concave meniscus has contact angle less than 90° and a convex meniscus has contact angle of greater than 90°. Water is a common Chemical substance that is essential for the survival of all known forms of Life. Diethyl ether, also known as ether and ethoxyethane, is a clear colorless and highly Flammable liquid with a low Boiling point and a Carbon tetrachloride, also known by many other names (see Table is the Organic compound with the formula CCl4 Acetic acid, also known as ethanoic acid, is an organic chemical compound, giving Vinegar its sour taste Water is a common Chemical substance that is essential for the survival of all known forms of Life. Iodomethane, commonly called Methyl iodide and commonly abbreviated "MeI" is the Chemical compound with the formula CH3I Mercury (ˈmɜrkjʊri also called quicksilver or hydrargyrum, is a Chemical element with the symbol Hg ( Latinized hydrargyrum For other uses see Meniscus (anatomy and lens (optics. Meniscus, plural menisci, from the Greek for "crescent" For other uses see Meniscus (anatomy and lens (optics. Meniscus, plural menisci, from the Greek for "crescent" ^[4]

This means that although the difference between the liquid-solid and solid-air surface tension, $\scriptstyle \gamma_\mathrm{ls} - \gamma_\mathrm{sa}$ , is difficult to measure directly, it can be inferred from the easily measured contact angle, $\scriptstyle \theta$ , if the liquid-air surface tension, $\scriptstyle \gamma_\mathrm{la}$ , is known.

This same relationship exists in the diagram on the right. But in this case we see that because the contact angle is less than 90°, the liquid-solid/solid-air surface tension difference must be negative:

$\gamma_\mathrm{la}\ >\ 0\ >\ \gamma_\mathrm{ls} - \gamma_\mathrm{sa}$

Special contact angles

Observe that in the special case of a water-silver interface where the contact angle is equal to 90°, the liquid-solid/solid-air surface tension difference is exactly zero.

Another special case is where the contact angle is exactly 180°. Water with specially prepared Teflon approaches this. Teflon is a Registered trademark and Brand name of the DuPont company for products made from three types of fluorine-containing polymers ( Fluoropolymers ^[1] Contact angle of 180° occurs when the liquid-solid surface tension is exactly equal to the liquid-air surface tension.

$\gamma_{\mathrm{la}}\ =\ \gamma_{\mathrm{ls}} - \gamma_\mathrm{sa}\ >\ 0\qquad \theta\ =\ 180^\circ$

Methods of measurement

Because surface tension manifests itself in various effects, it offers a number of paths to its measurement. Which method is optimum depends upon the nature of the liquid being measured, the conditions under which its tension is to be measured, and the stability of its surface when it is deformed.

Du Noüy Ring method: The traditional method used to measure surface or interfacial tension. Wetting properties of the surface or interface have little influence on this measuring technique. Maximum pull exerted on the ring by the surface is measured. ^[8]

A miniaturized version of Du Noüy method uses a small diameter metal needle instead of a ring, in combination with a high sensitivity microbalance to record maximum pull. The advantage of this method is that very small sample volumes (down to few tens of microliters) can be measured with very high precision, without the need to correct for buoyancy (for a needle or rather, rod, with proper geometry). Further, the measurement can be performed very quickly, minimally in about 20 seconds. First commercial multichannel tensiometers [CMCeeker] were recently built based on this principle.

Wilhelmy plate method: A universal method especially suited to check surface tension over long time intervals. A vertical plate of known perimeter is attached to a balance, and the force due to wetting is measured. ^[9]

Spinning drop method: This technique is ideal for measuring low interfacial tensions. The diameter of a drop within a heavy phase is measured while both are rotated.

Pendant drop method: Surface and interfacial tension can be measured by this technique, even at elevated temperatures and pressures. Geometry of a drop is analyzed optically. For details, see Drop. A drop or droplet is a small volume of Liquid, bounded completely or almost completely by Free surfaces Surface tension ^[9]

Surface tension can be measured using the pendant drop method on a goniometer. A goniometer is an instrument that either measures angle or allows an object to be rotated to a precise angular position

Bubble pressure method (Jaeger's method): A measurement technique for determining surface tension at short surface ages. Maximum pressure of each bubble is measured.

Drop volume method: A method for determining interfacial tension as a function of interface age. Liquid of one density is pumped into a second liquid of a different density and time between drops produced is measured. ^[10]

Capillary rise method: The end of a capillary is immersed into the solution. The height at which the solution reaches inside the capillary is related to the surface tension by the equation discussed below. ^[11]

Stalagmometric method: A method of weighting and reading a drop of liquid.

Sessile drop method: A method for determining surface tension and density by placing a drop on a substrate and measuring the contact angle (see Sessile drop technique). The density of a material is defined as its Mass per unit Volume: \rho = \frac{m}{V} Different materials usually have different The contact angle is the Angle at which a Liquid / Vapor interface meets the solid surface The sessile drop technique is a test performed to determine the Chemical affinity that a Liquid has to a Solid. ^[12]

Effects

Liquid in a vertical tube

Main article: Capillary action

Diagram of a Mercury Barometer

An old style mercury barometer consists of a vertical glass tube about 1 cm in diameter partially filled with mercury, and with a vacuum (called Toricelli's vacuum) in the unfilled volume (see diagram to the right). Capillary action, capillarity, capillary motion, or wicking is the ability of a substance to draw another substance into it Mercury (ˈmɜrkjʊri also called quicksilver or hydrargyrum, is a Chemical element with the symbol Hg ( Latinized hydrargyrum History The first barometer is thought to have been built unintentionally by Gasparo Berti, sometime between 1640 and 1643 Notice that the mercury level at the center of the tube is higher than at the edges, making the upper surface of the mercury dome-shaped. The center of mass of the entire column of mercury would be slightly lower if the top surface of the mercury were flat over the entire crossection of the tube. But the dome-shaped top gives slightly less surface area to the entire mass of mercury. Again the two effects combine to minimize the total potential energy. Such a surface shape is known as a convex meniscus. For other uses see Meniscus (anatomy and lens (optics. Meniscus, plural menisci, from the Greek for "crescent"

The reason we consider the surface area of the entire mass of mercury, including the part of the surface that is in contact with the glass, is because mercury does not adhere at all to glass. So the surface tension of the mercury acts over its entire surface area, including where it is in contact with the glass. If instead of glass, the tube were made out of copper, the situation would be very different. Mercury aggressively adheres to copper. So in a copper tube, the level of mercury at the center of the tube will be lower rather than higher than at the edges (that is, it would be a concave meniscus). In a situation where the liquid adheres to the walls of its container, we consider the part of the fluid's surface area that is in contact with the container to have negative surface tension. The fluid then works to maximize the contact surface area. So in this case increasing the area in contact with the container decreases rather than increases the potential energy. That decrease is enough to compensate for the increased potential energy associated with lifting the fluid near the walls of the container.

Illustration of capillary rise and fall. Red=contact angle less than 90°; blue=contact angle greater than 90°

If a tube is sufficiently narrow and the liquid adhesion to its walls is sufficiently strong, surface tension can draw liquid up the tube in a phenomenon known as capillary action. Capillary action, capillarity, capillary motion, or wicking is the ability of a substance to draw another substance into it The height the column is lifted to is given by:^[4]

$h\ =\ \frac {2\gamma_\mathrm{la} \cos\theta}{\rho g r}$

where

$\scriptstyle h$ is the height the liquid is lifted,
$\scriptstyle \gamma_\mathrm{la}$ is the liquid-air surface tension,
$\scriptstyle \rho$ is the density of the liquid,
$\scriptstyle r$ is the radius of the capillary,
$\scriptstyle g$ is the acceleration due to gravity,
$\scriptstyle \theta$ is the angle of contact described above. Note that if $\scriptstyle \theta$ is greater than 90°, as with mercury in a glass container, the liquid will be depressed rather than lifted.

Puddles on a surface

Profile curve of the edge of a puddle where the contact angle is 180°. The curve is given by the formula^[1] : $\scriptstyle x - x_0 \ = \ \frac {1} {2} H \cosh^{-1}\left(\frac {H}{h}\right) - H \sqrt{1 - \frac{h^2} {H^2}}$ where $\scriptstyle H \ = \ 2 \sqrt{\frac {\gamma} {g \rho}}$

Small puddles of water on a smooth clean surface have perceptible thickness.

Pouring mercury onto a horizontal flat sheet of glass results in a puddle that has a perceptible thickness (do not try this except under a fume hood. A puddle is a small accumulation of Liquid, usually Water, on a surface A fume hood or fume cupboard is a large piece of Scientific equipment common to Chemistry laboratories designed to limit a person's exposure to hazardous Mercury vapor is a toxic hazard). The puddle will spread out only to the point where it is a little under half a centimeter thick, and no thinner. Again this is due to the action of mercury's strong surface tension. The liquid mass flattens out because that brings as much of the mercury to as low a level as possible. But the surface tension, at the same time, is acting to reduce the total surface area. The result is the compromise of a puddle of a nearly fixed thickness.

The same surface tension demonstration can be done with water, but only on a surface made of a substance that the water does not adhere to. Wax is such a substance. Water poured onto a smooth, flat, horizontal wax surface, say a waxed sheet of glass, will behave similarly to the mercury poured onto glass.

The thickness of a puddle of liquid on a surface whose contact angle is 180° is given by:^[1]

$h\ =\ 2 \sqrt{\frac{\gamma} {g\rho}}$

where

$\scriptstyle h$ is the depth of the puddle in centimeters or meters.

$\scriptstyle \gamma$ is the surface tension of the liquid in dynes per centimeter or newtons per meter.

$\scriptstyle g$ is the acceleration due to gravity and is equal to 980 cm/s² or 9. 8 m/s²

$\scriptstyle \rho$ is the density of the liquid in grams per cubic centimeter or kilograms per cubic meter

Illustration of how lower contact angle leads to reduction of puddle depth

In reality, the thicknesses of the puddles will be slightly less than what is predicted by the above formula because very few surfaces have a contact angle of 180° with any liquid. When the contact angle is less than 180°, the thickness is given by:^[1]

$h\ =\ \sqrt{\frac{2\gamma_\mathrm{la}\left( 1 - \cos \theta \right)} {g\rho}}$

For mercury on glass, $\scriptstyle \gamma_\mathrm{Hg}\ =\ 487\ \mathrm{\frac{dyn}{cm}}$ , $\scriptstyle \rho_\mathrm{Hg}\ =\ 13.5\ \mathrm{\frac{g}{cm^3}}$ , and $\scriptstyle \theta = 140^\circ$ , which gives $\scriptstyle h_\mathrm{Hg}\ =\ 0.36\ \mathrm{cm}$ . For water on paraffin at 25 °C, $\scriptstyle \gamma_\mathrm{H_2O}\ =\ 72\ \mathrm{\frac{dyn}{cm}}$ , $\scriptstyle \rho_\mathrm{H_2O}\ = 1.0\ \mathrm{\frac{g}{cm^3}}$ , and $\scriptstyle \theta = 107^\circ$ which gives $\scriptstyle h_\mathrm{H_2O}\ =\ 0.44\ \mathrm{cm}$ .

The formula also predicts that when the contact angle is 0°, the liquid will spread out into a micro-thin layer over the surface. Such a surface is said to be fully wettable by the liquid.

The break up of streams into drops

Intermediate stage of a jet breaking into drops. Radii of curvature in the axial direction are shown. Equation for the radius of the stream is , where is the radius of the unperturbed stream, is the amplitude of the perturbation, is distance along the axis of the stream, and is the wave number

Intermediate stage of a jet breaking into drops. Radii of curvature in the axial direction are shown. Equation for the radius of the stream is $\scriptstyle R\left( z \right) = R_0 + A_k \cos \left( kz \right)$ , where $\scriptstyle R_0$ is the radius of the unperturbed stream, $\scriptstyle A_k$ is the amplitude of the perturbation, $\scriptstyle z$ is distance along the axis of the stream, and $\scriptstyle k$ is the wave number

In day to day life we all observe that a stream of water emerging from a faucet will break up into droplets, no matter how smoothly the stream is emitted from the faucet. This is due to a phenomenon called the Plateau-Rayleigh instability,^[1] which is entirely a consequence of the effects of surface tension. The Plateau-Rayleigh instability, often just called the Rayleigh instability, explains why and how a falling stream of fluid breaks up into smaller packets with the same volume

The explanation of this instability begins with the existence of tiny perturbations in the stream. These are always present, no matter how smooth the stream is. If the perturbations are resolved into sinusoidal components, we find that some components grow with time while others decay with time. Among those that grow with time, some grow at faster rates than others. Whether a component decays or grows, and how fast it grows is entirely a function of its wave number (a measure of how many peaks and troughs per centimeter) and the radius of the original cylindrical stream. The diagram to the right shows an exaggeration of a single component.

By assuming that all possible components exist initially in roughly equal (but minuscule) amplitudes, the size of the final drops can be predicted by determining by wave number which component grows the fastest. As time progresses, it is the component whose growth rate is maximum that will come to dominate and will eventually be the one that pinches the stream into drops. ^[3]

Although a thorough understanding of how this happens requires a mathematical development (see references^[1]^[3]), the diagram can provide a conceptual understanding. Observe the two bands shown girdling the stream – one at a peak and the other at a trough of the wave. At the trough, the radius of the stream is smaller, hence according to the Young-Laplace equation (discussed above) the pressure due to surface tension is increased. In Physics, the Young&ndashLaplace equation is a Nonlinear Partial differential equation that describes the Capillary pressure difference sustained Likewise at the peak the radius of the stream is greater and, by the same reasoning, pressure due to surface tension is reduced. If this were the only effect, we would expect that the higher pressure in the trough would squeeze liquid into the lower pressure region in the peak. In this way we see how the wave grows in amplitude over time.

But the Young-Laplace equation is influenced by two separate radius components. In Physics, the Young&ndashLaplace equation is a Nonlinear Partial differential equation that describes the Capillary pressure difference sustained In this case one is the radius, already discussed, of the stream itself. The other is the radius of curvature of the wave itself. The fitted arcs in the diagram show these at a peak and at a trough. Observe that the radius of curvature at the trough is, in fact, negative, meaning that, according to Young-Laplace, it actually decreases the pressure in the trough. Likewise the radius of curvature at the peak is positive and increases the pressure in that region. The effect of these components is opposite the effects of the radius of the stream itself.

The two effects, in general, do not exactly cancel. One of them will have greater magnitude than the other, depending upon wave number and the initial radius of the stream. When the wave number is such that the radius of curvature of the wave dominates that of the radius of the stream, such components will decay over time. When the effect of the radius of the stream dominates that of the curvature of the wave, such components grow exponentially with time.

When all the math is done, it is found that unstable components (that is, components that grow over time) are only those where the product of the wave number with the initial radius is less than unity ( $\scriptstyle kR_0 \ < \ 1$ ). The component that grows the fastest is the one whose wave number satisfies the equation:^[3]

$kR_0 \ \simeq \ 0.697$

Thermodynamics

As stated above, the mechanical work needed to increase a surface is $\scriptstyle dW \ = \ \gamma dA$ . Hence at constant temperature and pressure, surface tension equals Gibbs free energy per surface area:^[1]

$\gamma = \left( \frac{\partial G}{\partial A} \right)_{T,P,n}$

where $\scriptstyle G$ is Gibbs free energy and $\scriptstyle A$ is the area. In Thermodynamics, the Gibbs free energy ( IUPAC recommended name Gibbs energy or Gibbs function) is a Thermodynamic potential which

Thermodynamics requires that all spontaneous changes of state are accompanied by a decrease in Gibbs free energy.

From this it is easy to understand why decreasing the surface area of a mass of liquid is always spontaneous ( $\scriptstyle \Delta G \ < \ 0$ ), provided it is not coupled to any other energy changes. A spontaneous process is the time-evolution of a system in which it releases free energy (most often as heat and moves to a lower more thermodynamically stable energy state It follows that in order to increase surface area, a certain amount of energy must be added.

Gibbs free energy is defined by the equation,^[13] $\scriptstyle G \ = \ H \ - \ TS$ , where $\scriptstyle H$ is enthalpy and $\scriptstyle S$ is entropy. In Thermodynamics and molecular chemistry, the enthalpy (denoted as H, h, or rarely as χ) is a quotient or description of In Thermodynamics (a branch of Physics) entropy, symbolized by S, is a measure of the unavailability of a system ’s Energy Based upon this and the fact that surface tension is Gibbs free energy per unit area, it is possible to obtain the following expression for entropy per unit area:

$\left( \frac{\partial \gamma}{\partial T} \right)_{A,P}=-S^{A}$

Kelvin's Equation for surfaces arises by rearranging the previous equations. William Thomson 1st Baron Kelvin (or Lord Kelvin) OM, GCVO, PC, PRS, FRSE, (26 June 1824 &ndash 17 December 1907 It states that surface enthalpy or surface energy (different from surface free energy) depends both on surface tension and its derivative with temperature at constant pressure by the relationship. ^[14]

$H^A\ =\ \gamma - T \left( \frac {\partial \gamma}{\partial T} \right)_P$

Thermodynamics of soap bubble

The pressure inside a soap bubble can be derived from thermodynamic free energy considerations. At constant temperature and particle number, $d T = d N = 0$ , the differential Helmholtz free energy is given by

$dF\ = -PdV\ + \gamma dA$

where $P$ is the difference in pressure inside and outside of the bubble, and $γ$ is the surface tension. In equilbrium, $d F = 0$ , and so,

$PdV\ = \gamma dA$ .

For a spherical bubble, the volume and surface area are given simply by

$V = \frac{4}{3}\pi R^3 \rightarrow dV = 4\pi R^2 dR$ ,

and

$A = 4\pi R^2 \rightarrow dA = 8\pi R dR$ .

Substituting these relations into the previous expression, we find

$P = \frac{2}{R}\gamma$ ,

which is equivalent to the Young-Laplace equation when R_x = R_y.

Influence of temperature

Temperature dependency of the surface tension of benzene

Surface tension is dependent on temperature. Benzene, or benzol, is an organic Chemical compound and a known Carcinogen with the molecular formula C 6 H 6 For that reason, when a value is given for the surface tension of an interface, temperature must be explicitly stated. The general trend is that surface tension decreases with the increase of temperature, reaching a value of 0 at the critical temperature. The critical temperature, Tc of a material is the Temperature above which distinct Liquid and Gas phases do not exist For further details see Eötvös rule. The Eötvös rule, named after the Hungarian physicist Loránd (Roland Eötvös (1848-1919 enables the prediction of the Surface tension of an arbitrary There are only empirical equations to relate surface tension and temperature:

Eötvös:^[8]^[14]

$\gamma V^{2/3}=k(T_C-T)\,\!$

$\scriptstyle V$ is the molar volume of that substance
$\scriptstyle T_C$ is the critical temperature
$\scriptstyle k$ is a constant for each substance. The critical temperature, Tc of a material is the Temperature above which distinct Liquid and Gas phases do not exist

For example for water k = 1. 03 erg/°C (103 nJ/K), V = 18 ml/mol and T_C = 374 °C. The joule (written in lower case ˈdʒuːl or /ˈdʒaʊl/ (symbol J) is the SI unit of Energy measuring heat, Electricity The kelvin (symbol K) is a unit increment of Temperature and is one of the seven SI base units The Kelvin scale is a thermodynamic

A variant on Eötvös is described by Ramay and Shields:^[13]

$\gamma V^{2/3} = k\left(T_C - T - 6\right)$

where the temperature offset of 6 kelvins provides the formula with a better fit to reality at lower temperatures.

Guggenheim-Katayama:^[14]

$\gamma = \gamma^o \left( 1-\frac{T}{T_C} \right)^n$

$\scriptstyle \gamma^o$ is a constant for each liquid and n is an empirical factor, whose value is 11/9 for organic liquids. This equation was also proposed by van der Waals, who further proposed that $\scriptstyle \gamma^0$ could be given by the expression, $\scriptstyle K_2 T^{\frac {1}{3}}_c P^{\frac {2}{3}}_c$ , where $\scriptstyle K_2$ is a universal constant for all liquids, and $\scriptstyle P_c$ is the critical pressure of the liquid (although later experiments found $\scriptstyle K_2$ to vary to some degree from one liquid to another). The critical temperature, Tc of a material is the Temperature above which distinct Liquid and Gas phases do not exist ^[14]

Both Guggenheim-Katayama and Eötvös take into account the fact that surface tension reaches 0 at the critical temperature, whereas Ramay and Shields fails to match reality at this endpoint.

Influence of solute concentration

Solutes can have different effects on surface tension depending on their structure:

No effect, for example sugar
Increase of surface tension, inorganic salts
Decrease surface tension progressively, alcohols
Decrease surface tension and, once a minimum is reached, no more effect: surfactants

What complicates the effect is that a solute can exist in a different concentration at the surface of a solvent than in its bulk. Sugar is a class of edible Crystalline substances mainly Sucrose, Lactose, and Fructose. Traditionally inorganic compounds are considered to be of mineral not biological origin In Chemistry, an alcohol is any Organic compound in which a Hydroxyl group ( - O[[hydrogen H]]) is bound to a Carbon Surfactants are wetting agents that lower the Surface tension of a liquid allowing easier spreading and lower the Interfacial tension between two liquids This difference varies from one solute/solvent combination to another.

Gibbs isotherm states that:^[13] $\Gamma\ =\ - \frac{1}{RT} \left( \frac{\partial \gamma}{\partial \ln C} \right)_{T,P}$

$\scriptstyle \Gamma$ is known as surface concentration, it represents excess of solute per unit area of the surface over what would be present if the bulk concentration prevailed all the way to the surface. Gibbs isotherm is an equation which could be considered an Adsorption isotherm that connects Surface tension of a solution with the concentration of the solute It has units of mol/m²

$\scriptstyle C$ is the concentration of the substance in the bulk solution.

$\scriptstyle R$ is the gas constant and $\scriptstyle T$ the temperature

Certain assumptions are taken in its deduction, therefore Gibbs isotherm can only be applied to ideal (very dilute) solutions with two components. Relationship with the Boltzmann constant The Boltzmann constant kB (often abbreviated k) may be used in place of the gas constant by working Temperature is a physical property of a system that underlies the common notions of hot and cold something that is hotter generally has the greater temperature

Influence of particle size on vapour pressure

The Clausius-Clapeyron relation leads to another equation also attributed to Kelvin. The Clausius-Clapeyron relation, named after Rudolf Clausius and Émile Clapeyron, is a way of characterizing the Phase transition between two phases of It explains why, because of surface tension, the vapor pressure for small droplets of liquid in suspension is greater than standard vapor pressure of that same liquid when the interface is flat. Vapor pressure (also known as equilibrium vapor pressure or saturation vapor pressure) is the Pressure of a Vapor in equilibrium That is to say that when a liquid is forming small droplets, the equilibrium concentration of its vapor in its surroundings is greater. This arises because the pressure inside the droplet is greater than outside. ^[13]

$P_v^{fog}=P_v^o e^{\frac{V 2\gamma}{RT r_k}}$

Molecules on the surface of a tiny droplet (left) have, on average, fewer neighbors than those on a flat surface (right). Hence they are bound more weakly to the droplet than are flat-surface molecules.

$\scriptstyle P_v^o$ is the standard vapor pressure for that liquid at that temperature and pressure.
$\scriptstyle V$ is the molar volume.
$\scriptstyle R$ is the gas constant

$r k$ is the Kelvin radius, the radius of the droplets. Relationship with the Boltzmann constant The Boltzmann constant kB (often abbreviated k) may be used in place of the gas constant by working

The effect explains supersaturation of vapors. The term supersaturation refers to a Solution that contains more of the dissolved material than could be dissolved by the Solvent under normal circumstances In the absence of nucleation sites, tiny droplets must form before they can evolve into larger droplets. Nucleation is the onset of a Phase transition in a small region This requires a vapor pressure many times the vapor pressure at the phase transition point. In Thermodynamics, phase transition or phase change is the transformation of a thermodynamic system from one phase to another ^[13]

This equation is also used in catalyst chemistry to assess mesoporosity for solids. Catalysis is the process in which the rate of a Chemical reaction is increased by means of a Chemical substance known as a catalyst A mesoporous material is a material containing Pores with diameters between 2 and 50 nm ^[15]

The effect can be viewed in terms of the average number of molecular neighbors of surface molecules (see diagram).

The table shows some calculated values of this effect for water at different drop sizes:

P/P₀ for water drops of different radii at STP^[14]
Droplet radius (nm)	1000	100	10	1
P/P₀	1. In Physical sciences standard conditions for temperature and pressure are Standard sets of conditions for experimental measurements to allow comparisons to be made 001	1. 011	1. 114	2. 95

The effect becomes clear for very small drop sizes, as a drop of 1 nm radius has about 100 molecules inside, which is a quantity small enough to require a quantum mechanics analysis. Quantum mechanics is the study of mechanical systems whose dimensions are close to the Atomic scale such as Molecules Atoms Electrons

Gallery of effects

Breakup of a moving sheet of water bouncing off of a spoon.	Photo of flowing water adhering to a hand. Surface tension creates the sheet of water between the flow and the hand.	A soap bubble balances surface tension forces against internal pneumatic pressure. Pneumatics, Pressurized gas to affect mechanical motion Pneumatic power is used in Industry, where it is common to have factory units plumbed for Compressed Pressure (symbol 'p' is the force per unit Area applied to an object in a direction perpendicular to the surface	Surface tension prevents a coin from sinking: the coin is indisputably more dense than water, so it cannot be floating due to buoyancy alone. In Physics, buoyancy ( BrE IPA: /ˈbɔɪənsi/ is the upward Force on an object produced by the surrounding liquid or gas in which it is
A daisy. The entirety of the flower lies below the level of the (undisturbed) free surface. The water rises smoothly around its edge. Surface tension prevents the water from submerging the flower.	Photo showing the "tears of wine" phenomenon, which is induced by a combination of surface tension modification of water by ethanol together with ethanol evaporating faster than water. The phenomenon called tears of wine is manifested as a ring of clear liquid near the top of a glass of Wine, from which droplets form and flow back into the wine Evaporation is the process by which Molecules in a Liquid state (e	Fresh morning dew on a Water Horsetail (Equisetum fluviatile)	A metal paper clip floats on water. The Water Horsetail ( Equisetum fluviatile) also known as the Swamp Horsetail is a perennial Horsetail that commonly grows in dense colonies along

Data table

Surface tension of various liquids in dyn/cm against air^[16] Mixture %'s are by weight
Liquid	Temperature °C	Surface tension, γ
Acetic acid	20	27. and save the page --> This page provides supplementary chemical data on Acetic acid. 6
Acetic acid (40. 1%) + Water	30	40. 68
Acetic acid (10. 0%) + Water	30	54. 56
Acetone	20	23. and save the page -->This page provides supplementary chemical data on Acetone. 7
Diethyl ether	20	17. This page provides supplementary chemical data on Diethyl 0
Ethanol	20	22. &lbrace&lbracechembox supplement&rbrace&rbrace and save the page -->This page provides supplementary chemical data on Ethanol 27
Ethanol (40%) + Water	25	29. 63
Ethanol (11. 1%) + Water	25	46. 03
Glycerol	20	63
n-Hexane	20	18. This page provides supplementary chemical data on Glycerol This page provides supplementary chemical data on ''n''-hexane 4
Hydrochloric acid 17. Hydrochloric acid is the Solution of Hydrogen chloride ( H[[Chlorine Cl]] in water 7M aqueous solution	20	65. A molar Solution is one that contains one mole of solute per Litre of solution 95
Isopropanol	20	21. This page provides supplementary chemical data on Isopropanol. 7
Mercury	15	487
Methanol	20	22. Mercury (ˈmɜrkjʊri also called quicksilver or hydrargyrum, is a Chemical element with the symbol Hg ( Latinized hydrargyrum This page provides supplementary chemical data on Methanol. Material Safety Data Sheet 6
n-Octane	20	21. Octane is a straight-chain Alkane with the Chemical formula CH3(CH26CH3 8
Sodium chloride 6. For sodium chloride in the diet see Salt. Sodium chloride, also known as common salt, table salt, or Halite, is a 0M aqueous solution	20	82. A molar Solution is one that contains one mole of solute per Litre of solution 55
Sucrose (55%) + water	20	76. Solubility of Pure SucroseTemperature(Cg 45
Water	0	75. This page provides supplementary chemical data on water. Structure and properties 64
Water	25	71. 97
Water	50	67. 91
Water	100	58. 85

References

^ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j ^k Pierre-Gilles de Gennes, Françoise Brochard-Wyart, David Quéré (2002). The Weber number is a Dimensionless number in Fluid mechanics that is often useful in analysing fluid flows where there is an interface between two different fluids Capillary and Wetting Phenomena -- Drops, Bubbles, Pearls, Waves. Springer. ISBN 0-387-00592-7.
^ ^a ^b ^c White, Harvey E. (1948). Modern College Physics. van Nostrand. ISBN 0442294018.
^ ^a ^b ^c ^d John W. M. Bush (May 2004). MIT Lecture Notes on Surface Tension, lecture 5. Massachusetts Institute of Technology. Retrieved on April 1, 2007.
^ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j Sears, Francis Weston; Zemanski, Mark W. University Physics 2nd ed. Addison Wesley 1955
^ John W. M. Bush (April 2004). MIT Lecture Notes on Surface Tension, lecture 1. Massachusetts Institute of Technology. Retrieved on April 1, 2007.
^ John W. M. Bush (May 2004). MIT Lecture Notes on Surface Tension, lecture 3. Massachusetts Institute of Technology. Retrieved on April 1, 2007.
^ Aaronson, Scott, “NP-Complete Problems and physical reality.”, SIGACT News
^ ^a ^b Surface Tension by the Ring Method (Du Nouy Method) (pdf). PHYWE. Retrieved on 2007-09-08. Year 2007 ( MMVII) was a Common year starting on Monday of the Gregorian calendar in the 21st century. Events 70 - Roman forces under Titus sack Jerusalem. 1264 - The Statute of Kalisz
^ ^a ^b Surface and Interfacial Tension. Langmuir-Blodgett Instruments. Retrieved on 2007-09-08. Year 2007 ( MMVII) was a Common year starting on Monday of the Gregorian calendar in the 21st century. Events 70 - Roman forces under Titus sack Jerusalem. 1264 - The Statute of Kalisz
^ Surfacants at interfaces. lauda. de. Retrieved on 2007-09-08. Year 2007 ( MMVII) was a Common year starting on Monday of the Gregorian calendar in the 21st century. Events 70 - Roman forces under Titus sack Jerusalem. 1264 - The Statute of Kalisz
^ Calvert, James B. . Surface Tension (physics lecture notes). University of Denver. Retrieved on 2007-09-08. Year 2007 ( MMVII) was a Common year starting on Monday of the Gregorian calendar in the 21st century. Events 70 - Roman forces under Titus sack Jerusalem. 1264 - The Statute of Kalisz
^ Sessile Drop Method. Dataphysics. Retrieved on 2007-09-08. Year 2007 ( MMVII) was a Common year starting on Monday of the Gregorian calendar in the 21st century. Events 70 - Roman forces under Titus sack Jerusalem. 1264 - The Statute of Kalisz
^ ^a ^b ^c ^d ^e Moore, Walter J. (1962). Physical Chemistry, 3rd ed. . Prentice Hall.
^ ^a ^b ^c ^d ^e Adam, Neil Kensington (1941). The Physics and Chemistry of Surfaces, 3rd ed. . Oxford University Press.
^ G. Ertl, H. Knözinger and J. Weitkamp; Handbook of heterogeneous catalysis, Vol. 2, page 430; Wiley-VCH; Weinheim; 1997
^ Lange's Handbook of Chemistry, 10th ed. pp 1661–1665

External links

Dictionary

-noun

(physics) the effect on the surface of a liquid that makes it behave as a stretched elastic membrane; it is caused by unbalanced intermolecular forces
(physics) a measure of this effect

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Contents

Cause

Effects in everyday life

Basic physics

Two definitions

Water striders

Surface curvature and pressure

Liquid surface as a computer

Contact angles

Special contact angles

Methods of measurement

Effects

Liquid in a vertical tube

Puddles on a surface

The break up of streams into drops

Thermodynamics

Thermodynamics of soap bubble

Influence of temperature

Influence of solute concentration

Influence of particle size on vapour pressure

Gallery of effects

Data table

See also

References

External links

Dictionary

surface tension

-noun