11 minutes
CoverForewordUnit I. Atoms1. Introduction2. Matter3. Measurement4. The Atom5. Periodic Table6. Moles & Mass7. Light8. Blackbody Radiation, Photoelectric Effect9. Atomic Spectra, Bohr Model10. Orbitals & Quantum Numbers11. Electron Configurations12. Periodic TrendsUnit II. Molecules13. Bonding14. Nomenclature15. Lewis Structures Part 116. Lewis Structures Part 217. Molecular Shape18. Polarity19. Organic Molecules20. Isomers21. Valence Bond Theory22. Molecular Orbital TheoryUnit III. Interactions23. Pressure & Gas Laws24. Combined & Ideal Gas Laws25. Dalton's Law, Graham's Law, Henry's Law26. Kinetic Molecular Theory, Real Gases27. Intermolecular Forces28. Properties of Water29. Applications of IMF30. Phase DiagramsUnit IV. Reactions31. Stoichiometry32. Limiting Reactants, % Yield33. % Composition, Empirical Formulas34. Energy, Heat, and Work35. Calorimetry Part 136. Calorimetry Part 237. Enthalpy Part 138. Enthalpy Part 239. Entropy40. Gibb's Free Energy41. Climate and Human ImpactsKeywords
General College Chemistry
28

Properties of Water

The intermolecular forces between molecules in the liquid state vary depending upon their chemical identities and result in corresponding variations in various physical properties. Cohesive forces between like molecules are responsible for a liquid’s viscosity (resistance to flow) and surface tension (elasticity of a liquid surface). Adhesive forces between the molecules of a liquid and different molecules composing a surface in contact with the liquid are responsible for phenomena such as surface wetting and capillary rise. Because water is polar, it is an exceptionally good solvent. In part this is because it can interact using additional types of intermolecular forces. These include dipole-induced dipole interactions between polar and non-polar substances, and ion-dipole interactions between ions and polar substances.
Keywords: Intermolecular Forces, Liquid

28.1 Properties of Liquids

Learning Objectives

By the end of this section, you will be able to:

  • Distinguish between adhesive and cohesive forces
  • Define viscosity, surface tension, and capillary rise
  • Describe the roles of intermolecular attractive forces in each of these properties/phenomena

When you pour a glass of water, or fill a car with gasoline, you observe that water and gasoline flow freely. But when you pour syrup on pancakes or add oil to a car engine, you note that syrup and motor oil do not flow as readily. The viscosity of a liquid is a measure of its resistance to flow. Water, gasoline, and other liquids that flow freely have a low viscosity. Honey, syrup, motor oil, and other liquids that do not flow freely, like those shown in Figure 28.1, have higher viscosities. We can measure viscosity by measuring the rate at which a metal ball falls through a liquid (the ball falls more slowly through a more viscous liquid) or by measuring the rate at which a liquid flows through a narrow tube (more viscous liquids flow more slowly).

Figure 28.1

(a) Honey and (b) motor oil are examples of liquids with high viscosities; they flow slowly. (credit a: modification of work by Scott Bauer; credit b: modification of work by David Nagy)

Two photographs are shown and labeled “a” and “b.” Photo a shows a jar of honey with a dipper drizzling it onto a biscuit. More biscuits are shown in a basket in the background. Photo b shows the engine of a car and a person adding motor oil to the engine.

The IMFs between the molecules of a liquid, the size and shape of the molecules, and the temperature determine how easily a liquid flows. As Table 28.1 shows, the more structurally complex are the molecules in a liquid and the stronger the IMFs between them, the more difficult it is for them to move past each other and the greater is the viscosity of the liquid. As the temperature increases, the molecules move more rapidly and their kinetic energies are better able to overcome the forces that hold them together; thus, the viscosity of the liquid decreases.

Table 28.1

Viscosities of Common Substances at 25 °C

Substance Formula Viscosity (mPa·s)
water H2O 0.890
mercury Hg 1.526
ethanol C2H5OH 1.074
octane C8H18 0.508
ethylene glycol CH2(OH)CH2(OH) 16.1
honey variable ~2,000–10,000
motor oil variable ~50–500

The various IMFs between identical molecules of a substance are examples of cohesive forces. The molecules within a liquid are surrounded by other molecules and are attracted equally in all directions by the cohesive forces within the liquid. However, the molecules on the surface of a liquid are attracted only by about one-half as many molecules. Because of the unbalanced molecular attractions on the surface molecules, liquids contract to form a shape that minimizes the number of molecules on the surface—that is, the shape with the minimum surface area. A small drop of liquid tends to assume a spherical shape, as shown in Figure 28.2, because in a sphere, the ratio of surface area to volume is at a minimum. Larger drops are more greatly affected by gravity, air resistance, surface interactions, and so on, and as a result, are less spherical.

Figure 28.2

Attractive forces result in a spherical water drop that minimizes surface area; cohesive forces hold the sphere together; adhesive forces keep the drop attached to the web. (credit photo: modification of work by “OliBac”/Flickr)

A photo of a spider’s web with droplets of water attached to it is shown. Two images are shown the right of the photo and arrows lead from the photo to the images. The upper image shows twenty eight blue spheres stacked one atop the other in the bottom of a circular background. Five arrows are drawn pointing to the sides and downward from the sphere in the top middle of the drawing. The lower image shows another circular background of the same size as the first, but this time the blue spheres fill the image and are packed closely together. A sphere in the middle has six arrows pointing in all directions away from it.

Surface tension is defined as the energy required to increase the surface area of a liquid, or the force required to increase the length of a liquid surface by a given amount. This property results from the cohesive forces between molecules at the surface of a liquid, and it causes the surface of a liquid to behave like a stretched rubber membrane. Surface tensions of several liquids are presented in Table 28.2. Among common liquids, water exhibits a distinctly high surface tension due to strong hydrogen bonding between its molecules. As a result of this high surface tension, the surface of water represents a relatively “tough skin” that can withstand considerable force without breaking. A steel needle carefully placed on water will float. Some insects, like the one shown in Figure 28.3, even though they are denser than water, move on its surface because they are supported by the surface tension.

Table 28.3

Surface Tensions of Common Substances at 25 °C

Substance Formula Surface Tension (mN/m)
water H2O 71.99
mercury Hg 458.48
ethanol C2H5OH 21.97
octane C8H18 21.14
ethylene glycol CH2(OH)CH2(OH) 47.99

Figure 28.3

Surface tension (right) prevents this insect, a “water strider,” from sinking into the water.

A photo and a diagram as shown and a right-facing arrow leads from the photo to the image. The photo shows an insect standing on the surface of a sample of water. The image shows a square background that is two thirds covered in blue spheres that are closely packet together. A brown line starts at the upper left corner of the background and rests on top of the first row of spheres. The sphere directly under this low point of the line has four arrows drawn on it that face to both sides and downward. A sphere in the bottom center of the image has six arrows drawn on it that all face outward in different directions.

Surface tension is affected by a variety of variables, including the introduction of additional substances on the surface. In the late 1800s, Agnes Pockels, who was initially blocked from pursuing a scientific career but studied on her own, began investigating the impact and characteristics of soapy and greasy films in water. Using homemade materials, she developed an instrument known as a trough for measuring surface contaminants and their effects. With the support of renowned scientist Lord Rayleigh, her 1891 paper showed that surface contamination significantly reduces surface tension, and also that changing the characteristics of the surface (compressing or expanding it) also affects surface tension. Decades later, Irving Langmuir and Katharine Blodgett built on Pockels' work in their own trough and important advances in surface chemistry. Langmuir pioneered methods for producing single-molecule layers of film; Blodgett applied these to the development of non-reflective glass (critical for film-making and other applications), and also studied methods related to cleaning surfaces, which are important in semiconductor fabrication.

The IMFs of attraction between two different molecules are called adhesive forces. Consider what happens when water comes into contact with some surface. If the adhesive forces between water molecules and the molecules of the surface are weak compared to the cohesive forces between the water molecules, the water does not “wet” the surface. For example, water does not wet waxed surfaces or many plastics such as polyethylene. Water forms drops on these surfaces because the cohesive forces within the drops are greater than the adhesive forces between the water and the plastic. Water spreads out on glass because the adhesive force between water and glass is greater than the cohesive forces within the water. When water is confined in a glass tube, its meniscus (surface) has a concave shape because the water wets the glass and creeps up the side of the tube. On the other hand, the cohesive forces between mercury atoms are much greater than the adhesive forces between mercury and glass. Mercury therefore does not wet glass, and it forms a convex meniscus when confined in a tube because the cohesive forces within the mercury tend to draw it into a drop (Figure 28.4).

Figure 28.4

Differences in the relative strengths of cohesive and adhesive forces result in different meniscus shapes for mercury (left) and water (right) in glass tubes. (credit: Mark Ott)

This figure shows two test tubes. The test tube on the left contains mercury with a meniscus that rounds up. The test tube on the right contains water with a meniscus that rounds down.

If you place one end of a paper towel in spilled wine, as shown in Figure 28.5, the liquid wicks up the paper towel. A similar process occurs in a cloth towel when you use it to dry off after a shower. These are examples of capillary action—when a liquid flows within a porous material due to the attraction of the liquid molecules to the surface of the material and to other liquid molecules. The adhesive forces between the liquid and the porous material, combined with the cohesive forces within the liquid, may be strong enough to move the liquid upward against gravity.

Figure 28.5

Wine wicks up a paper towel (left) because of the strong attractions of water (and ethanol) molecules to the −OH groups on the towel’s cellulose fibers and the strong attractions of water molecules to other water (and ethanol) molecules (right). (credit photo: modification of work by Mark Blaser)

A photo and a diagram are shown. In the photo, a paper towel is dipped into a bowl full of a red liquid sitting on a countertop. The red liquid is traveling up the lower part of the paper towel, and this section of the photo has a square drawn around it. A right-facing arrow leads from this square to the image. The image is square and has a background of two types of molecules, mixed together. The first type of molecule is composed of two bonded black spheres, one of which is single bonded to three white spheres and one of which is single bonded to two white spheres and a red sphere that is itself bonded to a white sphere. The other type of molecule is composed of six black spheres bonded together in a row and bonded to other red and white spheres. Six upward-facing arrows are drawn on top of this background. They have positive signs on their lower ends and negative signs on their heads. Four upward-facing arrows are drawn with their signs reversed.

Towels soak up liquids like water because the fibers of a towel are made of molecules that are attracted to water molecules. Most cloth towels are made of cotton, and paper towels are generally made from paper pulp. Both consist of long molecules of cellulose that contain many −OH groups. Water molecules are attracted to these −OH groups and form hydrogen bonds with them, which draws the H2O molecules up the cellulose molecules. The water molecules are also attracted to each other, so large amounts of water are drawn up the cellulose fibers.

Capillary action can also occur when one end of a small diameter tube is immersed in a liquid, as illustrated in Figure 28.6. If the liquid molecules are strongly attracted to the tube molecules, the liquid creeps up the inside of the tube until the weight of the liquid and the adhesive forces are in balance. The smaller the diameter of the tube is, the higher the liquid climbs. It is partly by capillary action occurring in plant cells called xylem that water and dissolved nutrients are brought from the soil up through the roots and into a plant. Capillary action is the basis for thin layer chromatography, a laboratory technique commonly used to separate small quantities of mixtures. You depend on a constant supply of tears to keep your eyes lubricated and on capillary action to pump tear fluid away.

Figure 28.6

Depending upon the relative strengths of adhesive and cohesive forces, a liquid may rise (such as water) or fall (such as mercury) in a glass capillary tube. The extent of the rise (or fall) is directly proportional to the surface tension of the liquid and inversely proportional to the density of the liquid and the radius of the tube.

An image of two beakers and a tube is shown. The first beaker, drawn on the left and labeled “Water,” is drawn half-full of a blue liquid. Two open-ended capillary tubes are placed vertically in the beaker and inserted into the liquid. The liquid is shown higher in the tubes than in the beaker and is labeled “Capillary attraction.” The second beaker, drawn in the middle and labeled “Mercury,” is drawn half-full of a gray liquid. Two open-ended capillary tubes are placed vertically in the beaker and inserted into the liquid. The liquid is shown lower in the tubes than in the beaker and is labeled “Capillary repulsion.” Lines point to the vertical tubes and label them “Capillary tubes.” A separate drawing of one of the vertical tubes from the first beaker is shown on the right. A right-facing arrow leads from the liquid in the tube to a square call-out box that shows a close-up view of the liquid’s surface. The distance across the tube is labeled “2 r” in this image.

The height to which a liquid will rise in a capillary tube is determined by several factors as shown in the following equation:

h=2Tcosθrρgh=2Tcosθrρg

In this equation, h is the height of the liquid inside the capillary tube relative to the surface of the liquid outside the tube, T is the surface tension of the liquid, θ is the contact angle between the liquid and the tube, r is the radius of the tube, ρ is the density of the liquid, and g is the acceleration due to gravity, 9.8 m/s2. When the tube is made of a material to which the liquid molecules are strongly attracted, they will spread out completely on the surface, which corresponds to a contact angle of 0°. This is the situation for water rising in a glass tube.

Example 28.1

Capillary Rise

At 25 °C, how high will water rise in a glass capillary tube with an inner diameter of 0.25 mm?

For water, T = 71.99 mN/m and ρ = 1.0 g/cm3.

Solution

The liquid will rise to a height h given by: h=2Tcosθrρgh=2Tcosθrρg

The Newton is defined as a kg m/s2, and so the provided surface tension is equivalent to 0.07199 kg/s2. The provided density must be converted into units that will cancel appropriately: ρ = 1000 kg/m3. The diameter of the tube in meters is 0.00025 m, so the radius is 0.000125 m. For a glass tube immersed in water, the contact angle is θ = 0°, so cos θ = 1. Finally, acceleration due to gravity on the earth is g = 9.8 m/s2. Substituting these values into the equation, and cancelling units, we have:

h=2(0.07199kg/s2)(0.000125m)(1000kg/m3)(9.8m/s2)=0.12m=12 cmh=2(0.07199kg/s2)(0.000125m)(1000kg/m3)(9.8m/s2)=0.12m=12 cm

Check Your Learning

Water rises in a glass capillary tube to a height of 8.4 cm. What is the diameter of the capillary tube?

diameter = 0.36 mm

Chemistry in Everyday Life

Biomedical Applications of Capillary Action

Many medical tests require drawing a small amount of blood, for example to determine the amount of glucose in someone with diabetes or the hematocrit level in an athlete. This procedure can be easily done because of capillary action, the ability of a liquid to flow up a small tube against gravity, as shown in Figure 28.7. When your finger is pricked, a drop of blood forms and holds together due to surface tension—the unbalanced intermolecular attractions at the surface of the drop. Then, when the open end of a narrow-diameter glass tube touches the drop of blood, the adhesive forces between the molecules in the blood and those at the glass surface draw the blood up the tube. How far the blood goes up the tube depends on the diameter of the tube (and the type of fluid). A small tube has a relatively large surface area for a given volume of blood, which results in larger (relative) attractive forces, allowing the blood to be drawn farther up the tube. The liquid itself is held together by its own cohesive forces. When the weight of the liquid in the tube generates a downward force equal to the upward force associated with capillary action, the liquid stops rising.

Figure 28.7

Blood is collected for medical analysis by capillary action, which draws blood into a small diameter glass tube. (credit: modification of work by Centers for Disease Control and Prevention)

A photograph shows a person’s hand being held by a person wearing medical gloves. A thin glass tube is pressed against the persons finger and blood is moving up the tube.

Link to Supplemental Exercises

Supplemental exercises are available if you would like more practice with these concepts.

Citation of Previous Version

Flowers, P., Neth, E. J., Robinson, W. R., Theopold, K., & Langley, R. (2019). Chemistry in Context. In Chemistry: Atoms First 2e. OpenStax. https://openstax.org/books/chemistry-atoms-first-2e/pages/10-2-properties-of-liquids

28.2 Intermolecular Interactions in Mixtures

Ion-Dipole interactions

A dipole that is close to a positive or negative ion will orient itself so that the end whose partial charge is opposite to the ion charge will point toward the ion. This kind of interaction is very important in aqueous solutions of ionic substances; H2O is a highly polar molecule, so that in a solution of sodium chloride, for example, the Na+ ions will be enveloped by a shell of water molecules with their oxygen-ends pointing toward these ions, while H2O molecules surrounding the Cl ions will have their hydrogen ends directed inward. As a consequence of ion-dipole interactions, all ionic species in aqueous solution are hydrated; this is what is denoted by the suffix in formulas such as K+(aq), etc.

intermol_iondip.png
Figure 28.8: Ion-Dipole Interaction between a sodium ion and water

The strength of ion-dipole attraction depends on the magnitude of the dipole moment and on the charge density of the ion. This latter quantity is just the charge of the ion divided by its volume. Owing to their smaller sizes, positive ions tend to have larger charge densities than negative ions, and they should be more strongly hydrated in aqueous solution. The hydrogen ion, being nothing more than a bare proton of extremely small volume, has the highest charge density of any ion; it is for this reason that it exists entirely in its hydrated form H3O+ in water.

Dipole-induced dipole interactions

A permanent dipole can induce a temporary one in a species that is normally nonpolar, and thus produce a net attractive force between the two particles (Figure 28.9). This attraction is usually rather weak, but in a few cases it can lead to the formation of loosely-bound compounds. This effect explains the otherwise surprising observation that a wide variety of neutral molecules such as hydrocarbons, and even some of the noble gas elements, form stable hydrate compounds with water.

intermol_dipind.png
Figure 28.9: Dipole-induced dipole Interaction between a dipole and water

Citation of Previous Version

Lower, S. (2022). Intermolecular Interactions. In Chem1 (Lower). LibreTexts. https://chem.libretexts.org/Bookshelves/General_Chemistry/Book%3A_Chem1_(Lower)/07%3A_Solids_and_Liquids/7.02%3A_Intermolecular_Interactions

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