F321 Intermolecular Forces

Intermolecular Forces
Candidates should be able to: (k) describe the term electronegativity as the ability of an atom to attract the bonding electrons in a covalent bond; (l) explain that a permanent dipole may arise when covalently-bonded atoms have different electronegativities, resulting in a polar bond; (m) describe intermolecular forces based on permanent dipoles, as in hydrogen chloride, and induced dipoles (van der Waals forces), as in the noble gases; (n) describe hydrogen bonding, including the role of a lone pair, between molecules containing OH and NH groups, ie as in H2O, NH3 and analogous molecules; (o) describe and explain the anomalous properties of H2O resulting from hydrogen bonding, eg: (i) the density of ice compared with water, (ii) its relatively high freezing point and boiling point;

Dipoles Before we can understand intermolecular forces, we need to understand dipoles. A dipole arises as a result of charge separation. In chemistry the positive charge is all in the nucleus and does not move from there, but the negative charges are the electrons and these can get displaced from around the nucleus. When the "centre of gravity" of the negative charge is not the same place as the "centre of gravity" of the positive charge (the nucleus) then we have a dipole. We can imagine dipoles to be like small magnets, in that the positive end of one dipole attracts the negative end of another dipole. Dipoles attract one another electrostatically, in the same way as oppositely charged particles.

Intermolecular Forces There are three types of intermolecular forces that hold molecules (i.e. substances with simple molecular structures and covalent bonding, as opposed to giant ionic structures, giant covalent structures or metallic structures) together. The strength of the intermolecular forces is shown by the melting and boiling points the stronger the intermolecular forces, the more energy required to overcome them, and the higher the melting and boiling points. The intermolecular forces are (in order of increasing strength): 1) Van der Waals forces (weakest) 2) Dipole-dipole interactions 3) Hydrogen Bonding (strongest)

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F321 Intermolecular Forces Van der Waals forces If there were no forces between molecules, it would take no energy to separate them. Everything would be a gas, and the melting and boiling points would be absolute zero (0 Kelvin, equal to -273C). In reality even the noble gases, which are found as individual atoms, show variation in melting and boiling points. Evidence: Xe energy to vaporize (kJ mol-1) He Ar Ne 40 80 number of electrons Van der Waals forces are the weakest type of attraction between molecules, but EVERYTHING has them. They are properly called instantaneous dipole induced dipole interactions. The force arises because electrons are always moving (quickly, randomly within the space defined as their orbitals). At any moment in time it is possible for more electrons to lie on one side of the nucleus than the other. When this happens an instantaneous dipole is produced, with the nucleus the positive end of the dipole and the unbalanced electrons the negative end. The positive end of the instantaneous dipole attracts the electrons in neighboring atoms, causing an induced dipole in those atoms. The instantaneous dipole and induced dipole attract each other, resulting in a force of attraction between the atoms. The same effect occurs at a molecular level, molecules being attracted to other molecules are a result of the instantaneous dipole due to the random movement of electrons in one molecule causing an induced dipole in adjacent molecules. Comparing strength of Van der Waals forces Because they arise from the random movements of electrons, the more electrons there are the stronger the Van der Waals forces and the higher the melting and boiling point. If we are comparing two molecules, we need to count the total number of electrons in each to see which as more electrons and hence stronger Van der Waals forces. ISOELECTRONIC MOLECULES (i.e. having the same number of electrons) Because Van der Waals forces are SHORT-RANGE forces, the more the molecules can get close to one another, the stronger the Van der Waals forces will be. Linear molecules can achieve a greater area of surface contact than branched molecules with the same number of electrons, and so will have higher melting and boiling points. Kr Rn

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F321 Intermolecular Forces e.g. pentane boils at 36C 2,2-dimethylpropane boils at 10C

Check your understanding: Arrange the following groups of substances in order, highest boiling point first. i) Ne, He, Ar ii) propane, butane, pentane Permanent Dipole-Dipole Interactions A charged rod deflects flowing polar molecules. Non-polar molecules are not deflected. This is evidence for a further source of attraction that polar molecules have IN ADDITION to Van der Waals forces, but that non-polar molecules don't have. Polar molecules have a permanent dipole, and since dipoles attract, polar molecules attract one another. These dipole-dipole attractions are stronger than Van der Waals forces. Polar molecules therefore have higher melting and boiling points than similar nonpolar molecules. Evidence: N2 O2 NO m.p.(K) 63 55 110 non-polar molecule non-polar molecule polar molecule

To understand how these dipole-dipole interactions arise, we need to understand what gives a molecule a permanent dipole, making it a polar molecule: Electronegativity and Polar Bonds If both nuclei attract the bonding electrons in a covalent bond equally, the electrons occupy the space between the nuclei, and we have a perfect covalent bond e.g. Cl2. This is a nonpolar bond.

If one bonded atom attracts the bonding electrons more strongly than the other, because it is more electronegative, than we have a polar bond the electrons spend more time closer to the atom they are more attracted to: e.g. H2O, HCl, NH3

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F321 Intermolecular Forces

The symbols + and - mean a partial positive and a partial negative charge not as much as H+ or Cl- would be. The polar bond therefore has a dipole. Definition: Electronegativity is the ability of a bonded atom to attract the electrons in a covalent bond.

The more electronegative an atom is, the more it attracts the bonding electrons. It is therefore the DIFFERENCE in electronegativity between the two atoms in the bond which determines how polar the bond will be. Ionic and covalent are just the two extremes, with polar covalent bonds in between. small difference/no difference moderate difference very large difference pure covalent bond polar (covalent) bond ionic bond e.g. e.g. e.g. C-H C-Cl NaCl

We need to know how electronegative each of the atoms is in the bond to work out how polarized the bond will be, and what the resulting properties of the molecule will be. Trends in electronegativity: The top three most electronegative elements are F > O > N Electronegativity increases across a period from Group 1 to Group 7 (not 8!) Electronegativity decreases going down a group as atomic radius increases The electronegativity of hydrogen is lower than most non metals and higher than most metals. The electronegativity of carbon and hydrogen is approximately the same so C-H bonds are essentially non-polar. Molecules with permanent dipoles (polar molecules) We can use electronegativity to work out which bonds are polarized in a molecule. Whether the molecule has a permanent dipole then depends on whether the dipoles in the polar bonds balance or cancel each other out, given the 3-D shape of the molecule:

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F321 Intermolecular Forces Molecules with polar bonds are not necessarily polar molecules. Consider CO and CO2 as simple examples. CO has an overall dipole but CO2 does not. Both are linear molecules. + + -

O=C=O
got polar bonds dipoles cancel not polar molecule

C O
got polar bonds nothing to cancel or balance dipole polar molecule

Check your understanding: Consider the series of molecules CH4, CH3Cl, CH2Cl2, CHCl3 and CCl4 iii) Which of these contains polar bonds ? iv) Which of these molecules is polar ? v) Explain why the ammonium ion contains polar bonds but has no overall dipole vi) Arrange the following groups of substances in order, highest boiling point first. 1)
H H H H H C C C C H H H H H

2)
H

H H H C H H H H H H

3)

H H H H H C C C C H Cl H H H

4)

H H C C C H H H Cl

H C

What is the main type of interaction between the molecules in vii) hydrogen chloride (HCl) viii) hydrogen (H2) ix) Explain why pentane has a b.p. of 36C while 2-methylbutane has a b.p. of 28C Hydrogen Bonding is not really bonding, its still an intermolecular force, but it IS the strongest of all the intermolecular forces and results in some unexpected properties in substances which have it. A lot of biochemical systems/living systems depend on hydrogen bonding.

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F321 Intermolecular Forces When do we get hydrogen bonds ? Hydrogen bonds are a special case of dipole-dipole interactions. They occur between the lone pair on a very electronegative atom and a hydrogen atom which is + because it is bonded to a very electronegative atom. Rules for when hydrogen bonding occurs between two molecules: One molecule has a H-atom which is very highly positively polarized The other molecule has one of the very electronegative atoms fluorine, oxygen or nitrogen; and this atom has a lone pair available. BOTH OF THESE CRITERIA MUST BE MET TO GET A HYDROGEN BOND e.g. NH3 SiH4 HF HCl CH2O has hydrogen bonding no hydrogen bonding has hydrogen bonding no hydrogen bonding no hydrogen bonding (H is bonded to C, so not +)

Drawing a hydrogen bond: Draw the two molecules, show lone pairs Label the + and - atoms Show a H-bond from lone pair to + H atom Make hydrogen bond angle 180 Special properties of water - anomalously high boiling point and melting point - surface tension (forms droplets rather than spreading out) - ice floats (solids are usually more dense than same substance in liquid state) - water expands when it freezes (cracks containers in winter) In water - there are two lone pairs on the - O atom - there are two + H atoms - so each water molecule can form two hydrogen bonds - so networks and lattices of water molecules are possible

The strength of the hydrogen bonds which need to be overcome in ice before it can be melted give rise to the unusually high melting point. In the liquid state water molecules collect in hydrogen-bonded groups (clumps). These must be broken up and separated before water can be boiled and water vapour formed. The energy required to do this gives rise to the unusually high boiling point. At the surface, the water molecules form a 2-D network of hydrogen bonded water molecules this is the origin of surface tension, explaining Page 6

F321 Intermolecular Forces why a water droplet can stand up on a flat surface it is difficult to penetrate the surface because that requires breaking the network of hydrogen bonds. Also explains why pond-skaters can walk on water.

Ice is a 3-D hydrogen-bonded lattice. This is another example of an ordered, repeating structure in this case it is not a giant lattice but a SIMPLE MOLECULAR LATTICE, the molecules being held in the lattice by INTRAMOLECULAR FORCES. Each oxygen atom is covalently bonded to two hydrogen atoms, and hydrogen bonded to two other hydrogen atoms (via its lone pairs), in a tetrahedral arrangement. Each hydrogen atom is covalently bonded to one oxygen atom and hydrogen bonded to another. The hydrogen bonds (0.159nm) are LONGER than the covalent bonds (0.096nm), SPACING OUT the water molecules in the lattice its a more open structure than liquid water, so LESS DENSE. This is why ice floats, and why it expands when it freezes.

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F321 Intermolecular Forces Answers to "Check your understanding" questions: Arrange the following groups of substances in order, highest boiling point first. i) Ne, He, Ar Answer: Ar, Ne, He because Van der Waals forces increase with increasing number of electrons ii) propane, butane, pentane Answer: Pentane, Butane, Propane because Van der Waals forces increase with increasing size and therefore number of electrons Consider the series of molecules CH4, CH3Cl, CH2Cl2, CHCl3 and CCl4 iii) Which of these contains polar bonds ? Ans: all except CH4 iv) Which of these molecules is polar ? Ans: CH3Cl, CH2Cl2, and CHCl3 v) Explain why the ammonium ion contains polar bonds but has no overall dipole Ans: N and H have different electronegativities so the bonds are polar. The tetrahedral shape of the ammonium ion means that the dipoles are balanced symmetrically around the ions, so there is no overall dipole. vi)Arrange the following groups of substances in order, highest boiling point first. 1) CH3-CH2-CH2-CH3 2) CH3-C(CH3)2-H 3) CH3-CH2-CH2-CH2Cl 4) CH3-C(CH3)2-Cl Ans: 3 dipole-dipole, stronger VdW due to linear shape (more contact area) 4 dipole-dipole, weaker VdW due to less points of contact 1 no dipole-dipole, stronger VdW due to linear shape 2 no dipole-dipole, weaker VdW due to less points of contact What is the main type of interaction between molecules in vii) hydrogen chloride Ans: dipole-dipole (it is a polar molecule) viii) hydrogen Ans: VdW (no polar bonds) ix) Explain why pentane has a b.p. of 36C while 2-methylbutane has a b.p. of 28C: Ans: pentane molecules are more linear, less spherical there is more area of contact and hence stronger VdW forces.

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