Comparing Intermolecular Forces

For higher ionic strength, e g. highly saline waters the PITZER equation can be used (Pitzer 1973). This semi-empirical model is based also on the DEBYE-HUCKEL equation, but additionally integrates virial equations (vires = Latin for forces), that describe ion interactions (intermolecular forces). Compared with the ion dissociation theory the calculation is much more complicated and requires a... 

Solid CgQ is a redox-active array, with relatively weak intermolecular forces (comparable to interlayer forces in graphite). Therefore, it is a potential host for intercalation chemistry, like graphite or the transition metal sulfides. 

Rationalize the following differences in physical properties in terms of intermolecular forces. Compare the first three substances with each other, compare the last three with each othei and then compare all six. Can you account for any anomalies ... 

Isotactic polypropene has all of the methyl groups in front of the C—C—C chain viewing plane and all of the Hs behind as shown in Figure 1.12. This stereoregular structure maximizes the molecule-molecule contact and so increases the intermolecular forces compared to the atactic form. This regular structure is much stronger (than the atactic form above) and is used in sheet and film form for packaging and carpet fibers. 

Polyethylene. The crystal structure of this polymer is essentially the same as those of linear alkanes containing 20-40 carbon atoms, and the values of Tjj and AHf j are what would be expected on the basis of an extrapolation from data on the alkanes. Since there are no chain substituents or intermolecular forces other than London forces in polyethylene, we shall compare other polymers to it as a reference substance. 

When iodine chloride is heated to 27°C, the weak intermolecular forces are unable to keep the molecules rigidly aligned, and the solid melts. Dipole forces are still important in the liquid state, because the polar molecules remain close to one another. Only in the gas, where the molecules are far apart, do the effects of dipole forces become negligible. Hence boiling points as well as melting points of polar compounds such as Id are somewhat higher than those of nonpolar substances of comparable molar mass. This effect is shown in Table 9.3. 

We have now discussed three types of intermolecular forces dispersion forces, dipole forces, and hydrogen bonds. You should bear in mind that all these forces are relatively weak compared with ordinary covalent bonds. Consider, for example, the situation in HzO. The total intermolecular attractive energy in ice is about 50 kj/mol. In contrast, to dissociate one mole of water vapor into atoms requires the absorption of928 kj of energy, that is, 2(OH bond energy). This explains why it is a lot easier to boil water than to decompose it into the elements. Even at a temperature of 1000°C and 1 atm, only about one H20 molecule in a billion decomposes to hydrogen and oxygen atoms. 

We can assess the effect of intermolecular forces quantitatively by comparing the behavior of real gases with that expected of an ideal gas. One of the best ways of exhibiting these deviations is to measure the compression factor, Z, the ratio of the actual molar volume of the gas to the molar volume of an ideal gas under the same conditions ... 

Determine the vapor pressure of heavy water, D20, and of normal water at 25°G by using data in Appendix 2A. How do these values compare with each other Using your knowledge of intermolecular forces, explain the reason for the difference observed. 

Alkanes with long, unbranched chains tend to have higher melting points, boiling points, and enthalpies of vaporization than those of their branched isomers. The difference arises because, compared with unbranched molecules, the atoms of neighboring branched molecules cannot get as close together (Fig. 18.5). As a result, molecules with branched chains have weaker intermolecular forces than their unbranched isomers. 

The value o+l <0.4 found for H2 shows that even in the lowest state the molecules are rotating freely, the intermolecular forces producing only small perturbations from uniform rotation. Indeed, the estimated (3vq<135° corresponds to Fo <28 k, which is small compared with the energy difference 164 k of the rotational states j = 0 and j= 1, giving the frequency with which the molecule in either state reverses its orientation. The perturbation treatment shows that with this value of Fo the eigenfunctions and energy levels in all states closely approximate those for the free spatial rotator.9... 

All of these intermolecular forces influence several properties of polymers. Dispersion forces contribute to the factors that result in increased viscosity as molecular weight increases. Crystalline domains arise in polyethylene because of dispersion forces. As you will learn later in the text, there are other things that influence both viscosity and crystallization, but intermolecular forces play an important role. In polar polymers, such as polymethylmethacrylate, polyethylene terephthalate and nylon 6, the presence of the polar groups influences crystallization. The polar groups increase the intensity of the interactions, thereby increasing the rate at which crystalline domains form and their thermal stability. Polar interactions increase the viscosity of such polymers compared to polymers of similar length and molecular weight that exhibit low levels of interaction. 

Now, let s look at a polymeric system. To begin with, the motion in polymer chains is hindered. The massive size of the polymer itself and the intermolecular forces within the chains create an inflexible system, especially when compared to the aqueous systems with which we are most familiar. Secondly, the entropy of mixing is not actually as great as that seen in typical solution formation. Polymers are inherently highly entropic, so the benefit of mixing them together is modest. Therefore, any two polymers that form a miscible blend depend primarily... 

This structure contains a total of five bonds, which is an average of 2.5 bonds per NO unit. Therefore, there is no net increase in the number of bonds in the dimer compared to two separate molecules. The result is that there is not much energy advantage if dimers form. The melting point of NO is -164 °C and the boiling point is -152 °C. The low boiling point and small liquid range, about 12 °C, is indicative of only very weak intermolecular forces. The Lewis structure of the molecule can be shown as... 

Let s compare the intermolecular forces between I2 and Cl2. I2 has the greater molecular mass so the van der Waals forces between its molecules are greater in comparison with Cl2. Therefore at room temperature iodine is solid whereas chlorine is gas. 

The liquid state is a condensed state, so each molecule is always interacting with a group of neighbours although diffusing quite rapidly. As a result, although momentum through a shear plane still occurs, it is a small contribution when compared to the frictional resistance of the molecules in adjacent layers. It is the nature of this frictional resistance that we must now address and it will become clear that it arises from the intermolecular forces. The theories of the viscosity of liquids are still in an unfinished state but the physical ideas have been laid down. The first... 

---